Note: Within nine months of the publication of the mention of the grant of the European patent in the European PatentBulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with theImplementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has beenpaid. (Art. 99(1) European Patent Convention).

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(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention of the grant of the patent: 01.07.2009 Bulletin 2009/27

(21) Application number: 01961269.6

(22) Date of filing: 31.08.2001

(51) Int Cl.:C08G 81/02 (2006.01) C08L 101/00 (2006.01)

C08L 23/00 (2006.01)

(86) International application number: PCT/JP2001/007554

(87) International publication number: WO 2002/022713 (21.03.2002 Gazette 2002/12)

(54) BRANCHED POLYOLEFIN, PROCESS FOR PRODUCING THE SAME, AND THERMOPLASTIC RESIN COMPOSITION CONTAINING BRANCHED POLYOLEFIN

VERZWEIGTES POLYOLEFIN, VERFAHREN ZUR HERSTELLUNG DESSELBEN SOWIE DAS VERZWEIGTE POLYOLEFIN ENTHALTENDE THERMOPLASTISCHE HARZZUSAMMENSETZUNG

POLYOLEFINE RAMIFIEE, SON PROCEDE DE PRODUCTION ET COMPOSITION DE RESINE THERMOPLASTIQUE CONTENANT UNE POLYOLEFINE RAMIFIEE

(84) Designated Contracting States: BE DE FR GB IT NL

(30) Priority: 12.09.2000 JP 200027616412.09.2000 JP 2000276165

(43) Date of publication of application: 02.01.2003 Bulletin 2003/01

(73) Proprietor: Mitsui Chemicals, Inc.Tokyo (JP)

(72) Inventors: • Kojoh, Shinichi,

c/o Mitsui Chemicals, Inc.Sodegaura-shi,Chiba 299-0265 (JP)

• Matsugi, Tomoaki,c/o Mitsui Chemicals, Inc.Sodegaura-shi,Chiba 299-0265 (JP)

• Kashiwa, Norio,c/o Mitsui Chemicals, Inc.Sodegaura-shi,Chiba 299-0265 (JP)

(74) Representative: HOFFMANN EITLEPatent- und Rechtsanwälte Arabellastraße 481925 München (DE)

(56) References cited: EP-A- 0 366 412 EP-A- 0 856 541WO-A1-01/53369 JP-A- 7 011 003JP-A- 7 165 928 JP-A- 60 233 131US-A- 4 382 128 US-A- 4 592 960US-A- 4 727 120

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Description

FIELD OF THE INVENTION

[0001] The present invention relates to a branched polyolefin wherein at least one olefin chain is linked to a positionother than both ends of another olefin chain having an olefin composition which is the same as or different from that ofthe previous olefin chain, and relates to a process for preparing the branched polyolefin and a thermoplastic resincomposition containing the branched polyolefin.

BACKGROUND OF THE INVENTION

[0002] Since polyolefins have excellent processability, chemical resistance, electrical properties and mechanical prop-erties, they are processed into extruded articles, injection molded articles, blow molded articles, films, sheets, etc., andapplied to various uses.[0003] In recent years, property requirements for polyolefins have been diversified, and polyolefins of various prop-erties, e.g., polyolefins of excellent heat resistance and polyolefins having soft touch such as non-rigid polyvinyl chloride,are desired.[0004] As methods to improve the properties of polyolefins, there are a method of controlling the type of a monomeror the molar ratio between monomers, a method of changing monomer arrangement, such as random or block arrange-ment, etc., and various methods have been attempted heretofore.[0005] It is generally known that with respect to polyolefins containing ethylene as a main component, the polymer ofa branched structure exhibits specific melt properties and is advantageous in the polymer molding. On this account, withrespect to polyolefins containing an olefin of 3 or more carbon atoms as a main component, also the polymer of abranched structure is expected to have specific melt properties. When the composition of the olefin chain of the mainchain is different from that of the olefin chain of the side chain, the polymer is also expected to function as a compatibilizingagent.[0006] EP 0 366 412 is directed to a graft polymer comprising functionalized ethylene-alpha-olefin copolymer havingpolypropylene grafted thereto through one or more functional linkages. This document furthermore relates to a processfor making the graft polymer comprising combining the functionalized ethylene-alpha-olefin with maleated polypropylene.[0007] EP 0 856 541 is directed to a branched polyolefin in the form of a comb comprising a plurality of polyolefinarms linked to the polymer backbone. The branched polyolefin is prepared by coupling a polyolefin pre-arm with areactive polymeric backbone or polymerization of a polyolefin pre-arm, wherein the branched polyolefin has a melt flowindex (MFI) in the range of from 0.005 to 50 dg/min.[0008] Under such circumstances as described above, the present inventors have studied, and as a result the inventorshave found that a branched polyolefin wherein at least one olefin chain obtained from an olefin of 2 to 20 carbon atomsis linked to a position other than both ends of another olefin chain having an olefin composition which is the same as ordifferent from that of the previous olefin chain has various excellent properties. Based on the finding, the present inventionhas been accomplished.[0009] That is to say, it is an object of the present invention to provide a branched polyolefin having various excellentproperties and a process for preparing the same. It is another object of the invention to provide a thermoplastic resincomposition containing the branched polyolefin.

DISCLOSURE OF THE INVENTION

[0010] The branched polyolefin of the invention is a branched polyolefin comprising an olefin chain (A) having, asmain constituent units, recurring units obtained from at least one olefin selected from olefins of 2 to 20 carbon atomsand olefin chain (s) (B) having, as main constituent units, recurring units obtained from at least one olefin selected fromolefins of 2 to 20 carbon atoms and having an olefin composition which is the same as or different from that of the olefinchain (A), wherein the olefin chain (B) is linked to a position other than both ends of the olefin chain (A) through a bondhaving a carbonyl group, and at least one olefin chain (B) per one olefin chain (A) is present.[0011] The branched polyolefin of the invention is, for example, a polyolefin wherein the weight-average molecularweight (Mw) of the olefin chain (B) is not less than 5,000,a polyolefin wherein the bond having a carbonyl group is an ester bond and/or an amide bond,a polyolefin wherein one of the olefin chain (A) and the olefin chain (B) is a crystalline polyolefin and the other is a non-crystalline polyolefin,a polyolefin wherein both the olefin chain (A) and the olefin chain (B) are polypropylene, ora polyolefin wherein both the olefin chain (A) and the olefin chain (B) have stereoregularity.[0012] The process for preparing a branched polyolefin of the invention comprises allowing a functional group-con-

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taining polyolefin (C) having, as main constituent units, recurring units obtained from at least one olefin selected fromolefins of 2 to 20 carbon atoms and having one or more carboxyl groups and/or acid anhydride groups at positions otherthan both ends to react with a terminal modified polyolefin (D) having, as main constituent units, recurring units obtainedfrom at least one olefin selected from olefins of 2 to 20 carbon atoms, having an olefin composition which is the sameas or different from that of the functional group-containing polyolefin (C) and having at least one group capable of reactingwith a carboxyl group or an acid anhydride group at only the position of chain end to prepare the above-mentionedbranched polyolefin.[0013] The process for preparing a branched polyolefin of the invention is, for example,a process wherein the functional group-containing polyolefin (C) is a maleic anhydride-modified homopolymer or copol-ymer of ethylene and/or propylene,a process wherein the terminal modified polyolefin (D) is a one-side-end modified polyolefin having a group capable ofreacting with a carboxyl group or an acid anhydride group at only one-side-end, ora process wherein the terminal modified polyolefin (D) is a maleic anhydride-modified homopolymer or copolymer ofethylene and/or propylene.[0014] The thermoplastic resin composition of the invention contains the above-mentioned branched polyolefin in acontent of 0.01 to 50 % by weight.

PREFERRED EMBODIMENTS OF THE INVENTION

[0015] The branched polyolefin of the invention, the process for preparing the same and the thermoplastic resincomposition containing the branched polyolefin are described in detail hereinafter.[0016] The branched polyolefin of the invention comprises an olefin chain (A) having, as main constituent units,recurring units obtained from at least one olefin selected from olefins of 2 to 20 carbon atoms and olefin chain(s) (B)having, as main constituent units, recurring units obtained from at least one olefin selected from olefins of 2 to 20 carbonatoms and having an olefin composition which is the same as or different from that of the olefin chain (A), and the olefinchain (B) is linked to a position other than both ends of the olefin chain (A) through a bond having a carbonyl group.[0017] The meaning of the expression "composition is the same" is as follows. When the olefin chain (A) is for examplea homopolymer, the olefin chain (B) is a homopolymer composed of the same olefin as that of the olefin chain (A), andwhen the olefin chain (A) is for example a copolymer, the olefin chain (B) is a copolymer composed of the same combinationof olefins as that of the olefin chain (A) and having almost the same comonomer content as that of the olefin chain (A).The meaning of the expression "composition is different" is as follows. At least one condition selected from the monomertype for forming the olefin chain, the comonomer type and the comonomer content is different. In the present invention,it is preferable that the composition is different.[0018] The composition of the olefin chain (A) and the composition of the olefin chain (B) do not include the bondhaving a carbonyl group for linking the olefin chain (A) to the olefin chain (B).[0019] The olefin of 2 to 20 carbon atoms is, for example, a straight-chain or branched α-olefin or a cycloolefin.[0020] Examples of the straight-chain α-olefins include those of 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms,such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hex-adecene, 1-octadecene and 1-eicosene.[0021] Examples of the branched α-olefins include those of 4 to 20 carbon atoms, preferably 5 to 10 carbon atoms,such as 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene and 3-ethyl-1-hexene.[0022] Examples of the cycloolefins include those of 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such ascyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene and vinylcyclohexane.[0023] When the composition of the olefin chain (A) and the composition of the olefin chain (B) are the same, the olefinchain (A) and the olefin chain (B) preferably have recurring units obtained from an olefin of 3 to 20 carbon atoms asmain constituent units.[0024] Although the olefin chain (A) and the olefin chain (B) have recurring units obtained from an olefin of 2 to 20carbon atoms as main constituent units, they may contain recurring units obtained from a polymerizable monomer otherthan the olefin of 2 to 20 carbon atoms, such as a diene.[0025] The olefin chain (A) and the olefin chain (B) may be formed from recurring units obtained from one olefinselected from the above olefins of 2 to 20 carbon atoms, or may be formed from recurring units obtained from two ormore olefins selected from the above olefins of 2 to 20 carbon atoms.[0026] When the olefin chain (A) and the olefin chain (B) are formed from recurring units obtained from two or moreolefins selected from the above olefins of 2 to 20 carbon atoms, one of the olefins is desired to be contained in a contentof usually not less than 60 % by mol and less than 100 % by mol, preferably 70 to 99 % by mol, more preferably 75 to98 % by mol, and the other is an olefin selected from olefins of 2 to 20 carbon atoms other than the olefin describedabove and/or a polymerizable monomer other than the olefin of 2 to 20 carbon atoms.

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[0027] The olefin chain (A) and the olefin chain (B) may have stereoregularity, and in this case, they may be any ofisotactic and syndiotactic.[0028] When the composition of the olefin chain (A) is the same as that of the olefin chain (B), the olefin chain (A) andthe olefin chain (B) are preferably polypropylene, such as a propylene homopolymer or a propylene copolymer composedof propylene and an olefin of 4 to 20 carbon atoms, particularly preferably a propylene homopolymer. The olefin chain(A) and the olefin chain (B) preferably have stereoregularity, and in this case, they may be any of isotactic and syndiotactic.When the olefin chain (A) and the olefin chain (B) have stereoregularity, the olefin chain (A) and the olefin chain (B) arepreferably isotactic.[0029] When the composition of the olefin chain (A) is different from that of the olefin chain (B), it is preferable thatone of the olefin chain (A) and the olefin chain (B) is a crystalline polyolefin and the other is a non-crystalline polyolefin.It is particularly preferable that the olefin chain (A) is a non-crystalline copolymer of ethylene and an olefin of 3 to 20carbon atoms, such as an ethylene/propylene copolymer, or a non-crystalline copolymer of propylene and an olefin of2 to 20 carbon atoms other than propylene, such as a propylene/ethylene copolymer, and that the olefin chain (B) is acrystalline polymer such as an ethylene homopolymer or a propylene homopolymer.[0030] When the olefin composition of the olefin chain (A) is different from that of the olefin chain (B) in the branchedpolyolefin of the invention, examples of the olefin chains are as follows. When the olefin chain (A) is for example ahomopolymer, the olefin chain (B) is a homopolymer or copolymer comprising a different olefin from that of the olefinchain (A), and when the olefin chain (A) is a copolymer, the olefin chain (B) is a copolymer of a different combination ofolefins from that of the olefin chain (A) or a copolymer having the same combination of olefins as that of the olefin chain(A) but having a different monomer ratio, or a homopolymer.[0031] The olefin chain (A) has a weight-average molecular weight (Mw) of usually 10,000 to 10,000,000, preferably20,000 to 5,000,000, more preferably 50,000 to 1,000,000.[0032] The olefin chain (B) preferably has 15 or more carbon atoms and has a weight-average molecular weight (Mw)of usually not less than 5,000, preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000.[0033] When the composition of the olefin chain (A) is different from that of the olefin chain (B), the weight-averagemolecular weight (Mw) of the olefin chain (B) is desired to be usually not less than 5,000, preferably 10,000 to 10,000,000,more preferably 15,000 to 1,000,000, still more preferably 20,000 to 500,000.[0034] In the branched polyolefin of the invention, the olefin chain (B) is linked to a position other than both ends ofthe olefin chain (A) through a bond having a carbonyl group, and the number of the olefin chains (B) linked to the olefinchain (A) is not less than 1, preferably not less than 1.1, more preferably 1.5 to 100, still more preferably 2 to 50, basedon one olefin chain (A).[0035] Examples of the bonds having a carbonyl group include an ester bond, an amide bond, an imide bond, aurethane bond and a urea bond.[0036] These bonds may be present singly or in combination of two or more kinds, and an ester bond and/or an amidebond is preferable.[0037] The branched polyolefin of the invention has a melt flow rate (MFR, measured at 190°C or 230°C under a loadof 2.16 kg in accordance with ASTM D 1238, the same shall apply hereinafter) of usually 0.001 to 3,000 g/10 min,preferably 0.005 to 1,000 g/10 min, more preferably 0.01 to 1,000 g/10 min, and a density (measured in accordancewith ASTM D 1505, the same shall apply hereinafter) of usually 0.79 to 1.0 g/cm3, preferably 0.75 to 0.98 g/cm3, morepreferably 0.80 to 0.96 g/cm3.[0038] When the composition of the olefin chain (A) is the same as that of the olefin chain (B), MFR of the branchedpolyolefin is desired to be in the range of usually 0.01 to 3,000 g/10 min, preferably 0.05 to 1,000 g/10 min, more preferably0.1 to 500 g/10 min. When the composition of the olefin chain (A) is different from that of the olefin chain (B), MFR ofthe branched polyolefin is desired to be in the range of usually 0.001 to 1,000 g/10 min, preferably 0.005 to 500 g/10min, more preferably 0.01 to 100 g/10 min.[0039] Examples of preferred combinations of the olefin (A) and the olefin (B) are described below.[0040] When the composition of the olefin chain (A) is the same as that of the olefin chain (B), the olefin chain (A) andthe olefin chain (B) are preferably polypropylene, and in this case, the polypropylene preferably has a density of 0.880to 0. 960 g/cm3, particularly 0.890 to 0.950 g/cm3, and MFR of 0.05 to 1,000 g/10 min, particularly 0.1 to 500 g/10 min.When the polypropylene is a copolymer, the content of the copolymerized component is desired to be usually not morethan 10 % by mol, particularly not more than 5 % by mol.[0041] When the composition of the olefin chain (A) is different from that of the olefin chain (B), it is preferable thatthe olefin chain (A) is a copolymer of ethylene and an olefin of 3 to 20 carbon atoms and the olefin chain (B) is polypropylene.In this case, the copolymer of ethylene and an olefin of 3 to 20 carbon atoms, that is the olefin chain (A), has a densityof 0.850 to 0.900 g/cm3, preferably 0.858 to 0.898 g/cm3, more preferably 0.855 to 0.895 g/cm3, MFR of 0.1 to 50 g/10min, preferably 0.2 to 40 g/10 min, more preferably 0.3 to 30 g/10 min, and a crystallinity, as measured by X rays, ofless than 30 %, preferably less than 28 %, more preferably less than 25 %. The polypropylene, that is the olefin chain(B), preferably has a density of 0.880 to 0.960 g/cm3, particularly 0.890 to 0.950 g/cm3, and MFR of 0.05 to 1,000 g/10

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min, particularly 0.1 to 500 g/10 min. When the polypropylene is a copolymer, the content of the copolymerized componentis desired to be usually not more than 10 % by mol, particularly not more than 5 % by mol.

Preparation

[0042] The branched polyolefin of the invention is prepared by allowing a functional group-containing polyolefin (C)having, as main constituent units, recurring units obtained from at least one olefin selected from olefins of 2 to 20 carbonatoms and having one or more carboxyl groups and/or acid anhydride groups at positions other than both ends to reactwith at least one terminal modified polyolefin (D) having, as main constituent units, recurring units obtained from at leastone olefin selected from olefins of 2 to 20 carbon atoms, having an olefin composition which is the same as or differentfrom that of the olefin chain (C) and having at least one group capable of reacting with a carboxyl group or an acidanhydride group at only the position of chain end.

(C) Functional group-containing polyolefin

[0043] The functional group-containing polyolefin (C) is a polyolefin having one or more carboxyl groups and/or acidanhydride groups at positions other than both ends. The functional group-containing polyolefin (C) becomes the olefinchain (A), and the carboxyl group and/or the acid anhydride group becomes a bond having a carbonyl group for linkingthe olefin chain (A) to the olefin chain (B).[0044] The functional group-containing polyolefin (C) is obtained by graft modifying a part or the whole of an unmodifiedpolyolefin with an unsaturated carboxylic acid or its derivative.[0045] The unmodified polyolefin can be prepared by polymerizing or copolymerizing the aforesaid olefin of 2 to 20carbon atoms using a hitherto known catalyst. Examples of the hitherto known catalysts include a magnesium-supportedtitanium catalyst system and a metallocene catalyst.[0046] These catalysts are described below.

Magnesium-supported titanium catalyst system

[0047] The magnesium-supported titanium catalyst system is preferably a catalyst system comprising a solid titaniumcatalyst component (I) containing titanium, magnesium and halogen as essential ingredients, an organometallic com-pound catalyst component (II), and if necessary, an electron donor (III).

(I) Solid titanium catalyst component

[0048] The solid titanium catalyst component (I) can be prepared by contacting the below-described magnesiumcompound, titanium compound and electron donor with each other.

Magnesium compound

[0049] The magnesium compound is a magnesium compound having reducing ability or a magnesium compoundhaving no reducing ability.[0050] The magnesium compound having reducing ability is, for example, an organomagnesium compound repre-sented by the following formula:

XnMgR2-n

wherein n is a number of 0�n<2, R is hydrogen, an alkyl group of 1 to 20 carbon atoms, an aryl group or a cycloalkylgroup, when n is 0, two of R may the same or different, and X is a halogen.[0051] Examples of the organomagnesium compounds having reducing ability include alkylmagnesium compounds,such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexyl-magnesium, didecylmagnesium, octylbutylmagnesium and ethylbutylmagnesium; alkylmagnesium halides, such asethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride and amyl-magnesium chloride; alkylmagnesium alkoxides, such as butylethoxymagnesium, ethylbutoxymagnesium and octylbu-toxymagnesium; butylmagnesium hydride; and magnesium hydride.[0052] Metallic magnesium is also employable.[0053] Examples of the magnesium compounds having no reducing ability include magnesium halides, such as mag-nesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; alkoxymagnesium halides, such asmethoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride

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and octoxymagnesium chloride; aryloxymagnesium halides, such as phenoxymagnesium chloride and methylphenox-ymagnesium chloride; dialkoxymagnesiums, such as diethoxymagnesium, diisopropoxymagnesium, dibutoxymagnesi-um, di-n-octoxymagnesium, di-2-ethylhexoxymagnesium and methoxyethoxymagnesium; diaryloxymagnesiums, suchas diphenoxymagnesium, dimethylphenoxymagnesium and phenoxymethylphenoxymagnesium; and carboxylic acidsalts of magnesium, such as magnesium laurate and magnesium stearate.[0054] The magnesium compound having no reducing ability may be a compound derived from the magnesium com-pound having reducing ability or a compound derived during the preparation of the catalyst component. In order to derivethe magnesium compound having no reducing ability from the magnesium compound having reducing ability, the mag-nesium compound having reducing ability has only to be contacted with, for example, a polysiloxane compound, ahalogen-containing silane compound, a halogen-containing aluminum compound, en ester, an alcohol, a halogen-con-taining compound or a compound having an OH group or an active carbon-oxygen bond.[0055] The magnesium compound having reducing ability and the magnesium compound having no reducing abilitymayforma complex compound or a double compound together with another metal such as aluminum, zinc, boron, beryllium,sodium or potassium, or may be a mixture of the magnesium compound and another metallic compound. The magnesiumcompounds may be used singly or in combination of two or more kinds.[0056] Of the above magnesium compounds, a solid magnesium compound can be made liquid by the use of anelectron donor (i). Examples of the electron donors (i) include alcohols, phenols, ketones, aldehydes, ethers, amines,pyridines and metallic acid esters.[0057] Specifically, there can be mentioned:

alcohols of 1 to 18 carbon atoms, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol,octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylalcohol and isopropylbenzyl alcohol;halogen-containing alcohols of 1 to 18 carbon atoms, such as trichloromethanol, trichloroethanol and trichlorohex-anol;alkoxy alcohols, such as 2-propoxyethanol, 2-butoxyethanol, 2-ethoxypropanol, 3-ethoxypropanol, 1-methoxybuta-nol, 2-methoxybutanol and 2-ethoxybutanol;phenols of 6 to 20 carbon atoms, which may have a lower alkyl group, such as phenol, cresol, xylenol, ethylphenol,propylphenol, nonylphenol, cumylphenol and naphthol;ketones of 3 to 15 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone,benzophenone and benzoquinone;aldehydes of 2 to 15 carbon atoms, such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolual-dehyde and naphthaldehyde;ethers of 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahy-drofuran, anisole and diphenyl ether;amines, such as trimethylamine, triethylamine, tributylamine, tribenzylamine and tetramethylethylenediamine; andpyridines, such as pyridine, methylpyridine, ethylpyridine and dimethylpyridine; andmetallic acid esters, such as tetraethoxytitanium, tetra-n-propoxytitanium, tetra-i-propoxytitanium, tetrabutoxytitani-um, tetrahexoxytitanium, tetrabutoxyzirconium and tetraethoxyzirconium.

[0058] These may be used singly or in combination of two or more kinds.[0059] Of these, alcohols, alkoxy alcohols and metallic acid esters are particularly preferably employed. The solubili-zation reaction of the solid magnesium compound by the electron donor (i) is generally carried out by contacting thesolid magnesium compound with the electron donor (i), followed by heating if necessary. In this case, the contacttemperature is in the range of 0 to 200°C, preferably 20 to 180°C, more preferably 50 to 150°C.[0060] In the solubilization reaction, a hydrocarbon solvent or the like may be present. Examples of the hydrocarbonsolvents include aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, decane, dodecane, tetradecaneand kerosine; alicyclic hydrocarbons, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane,cyclooctane and cyclohexene; aromatic hydrocarbons, such as benzene, toluene and xylene; and halogenated hydro-carbons, such as dichloroethane, dichloropropane, trichloroethylene, chlorobenzene and 2,4-dichlorotoluene.[0061] As the magnesium compound used for preparing the solid titanium catalyst component (I), many magnesiumcompounds other than those described above are also employable. In the solid titanium catalyst component (I) finallyobtained, however, the magnesium compound is preferably present in the form of a halogen-containing magnesiumcompound. Therefore, if a magnesium compound containing no halogen is used, it is preferable to contact the magnesiumcompound with a halogen-containing compound during the course of the preparation.[0062] Of the above compounds, magnesium compounds having no reducing ability are preferably contained in thecomponent (I), and of these, halogen-containing magnesium compounds are particularly preferably contained. Of these,magnesium chloride, alkoxymagnesium chloride or aryloxymagnesium chloride is preferably contained.

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Titanium compound

[0063] As the titanium compound, a tetravalent titanium compound is preferably employed. The tetravalent titaniumcompound is, for example, a compound represented by the following formula:

Ti (OR)gX4-g

wherein R is a hydrocarbon group, X is a halogen, and 0�g �4.[0064] Examples of such compounds include:

titanium tetrahalides, such as TiCl4, TiBr4 and TiI4;alkoxytitanium trihalides, such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(O-n-C4H9)Cl3, Ti(OC2H5)Br3 and Ti(O-iso-C4H9)Br3;dialkoxytitanium dihalides, such as Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2, Ti(O-n-C4H9)2Cl2 and Ti(OC2H5)2Br2;trialkoxytitanium monohalides, such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(O-n-C4H9)3Cl and Ti(OC2H5)3Br; andtetraalkoxytitaniums, such as Ti(OCH3)4, Ti(OC2H5)4, Ti(O-n-C4H9)4, Ti(O-iso-C4H9)4 and Ti(O-2-ethylhexyl)4.

[0065] Of these, titanium tetrahalides are preferable, and titanium tetrachloride is particularly preferable. These titaniumcompounds may be used singly or in combination of two or more kinds. The titanium compound may be used togetherwith an aromatic hydrocarbon, or may be used, diluting with a hydrocarbon or a halogenated hydrocarbon.

(ii) Electron donor

[0066] In the preparation of the solid titanium catalyst component (I), an electron donor (ii) is preferably employed.Examples of the electron donors (ii) include the following acid halides, acid amides, nitriles, acid anhydrides, organicacid esters and polyethers.[0067] Specifically, there can be mentioned:

acid halides of 2 to 15 carbon atoms, such as acetyl chloride, benzoyl chloride, toluyl chloride and anisoyl chloride;acid amides, such as N,N-dimethylacetamide, N,N-diethylbenzamide and N,N-dimethyltoluamide;nitriles, such as acetonitrile, benzonitrile and tolunitrile;acid anhydrides, such as acetic anhydride, phthalic anhydride and benzoic anhydride; andorganic acid esters of 2 to 18 carbon atoms, such as methyl formate, methyl acetate, ethyl acetate, vinyl acetate,propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroa-cetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate,ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzylbenzoate, methyl toluylate, ethyl toluylate, amyl toluylate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl-ethoxybenzoate, γ-butyrolactone, δ-valerolactone, cumarin, phthalide and ethyl carbonate.

[0068] Preferred examples of the organic esters include polycarboxylates having skeletons represented by the followingformulas:

[0069] In the above formulas, R1 is a substituted or unsubstituted hydrocarbon group, and R2, R5 and R6 are hydrogenor a substituted or unsubstituted hydrocarbon group. R3 and R4 are hydrogen or a substituted or unsubstituted hydro-

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carbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. R3 and R4 maybe bonded to form a cyclic structure. The substituent of the substituted hydrocarbon groups R1 to R6 has a hetero atomsuch as N, O or S, and has, for example, a group of C-O-C, COOR, COOH, OH, SO3H, -C-N-Cor NH2.[0070] Examples of such polycarboxylates include aliphatic polycarboxylates, alicyclic polycarboxylates, aromaticpolycarboxylates and heterocyclic polycarboxylates.[0071] Preferred examples of the polycarboxylates having skeletons represented by the above formulas include:

diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diaryl methylsuccinate, diisobutyl α-methylglutarate,diisopropyl β-methylglutarate, diisobutyl methylmalonate, dibutyl ethylmalonate, diethyl ethylmalonate, diethyl iso-propylmalonate, dibutyl isopropylmalonate, dibutyl butylmalonate, dibutyl phenylmalonate, diethyl diethylmalonate,dibutyl dibutylmalonate, diethyl dibutylmalonate, n-butyl maleate, dibutylmethylmaleate, dibutylbutylmaleate, di-2-ethylhexyl fumarate, di-n-hexyl cyclohexenecaboxylate, diethyl nadiate, diisopropyl tetrahydrophthalate, diethylphthalate, monoethylphthalate, dipropylphthalate, diisobutylphthalate, diisopropyl phthalate, ethylisobutyl phthalate,di-n-butyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, di(2-methylpentyl) phtha-late, di(3-methylpentyl) phthalate, di(4-methylpentyl) phthalate, di(2,3-dimethylbutyl) phthalate, di(3-methylhexyl)phthalate, di(4-methylhexyl) phthalate, di(5-methylhexyl) phthalate, di(3-ethylpentyl) phthalate, di(3,4-dimethyl-pentyl) phthalate, di(2,4-dimethylpentyl) phthalate, di(2-methylhexyl) phthalate, di(2-methyloctyl) phthalate, didecylphthalate, diphenyl phthalate and mixtures of these phthalic acid diesters; anddiethyl naphthalenedicarboxylate, dibutyl naphthalenedicarboxylate, triethyl trimellitate, tributyl trimellitate, dibutyl3,4-furandicarboxylate, diethyl adipate, dibutyl adipate, dioctyl sebacate and dibutyl sebacate.

[0072] Of these, phthalic acid diesters are preferably employed.[0073] Also employable as the electron donor is a compound having two or more ether bonds present through pluralatoms (sometimes referred to as a "polyether" hereinafter). The polyether is, for example, a compound wherein theatoms present between the ether bonds are carbon, silicon, oxygen, nitrogen, phosphorus, boron and sulfur, or two ormore atoms selected from these atoms. Such a compound is preferably a compound wherein relatively bulky substituentsare bonded to the atoms between the ether bonds and the atoms present between two or more ether bonds includeplural carbon atoms, e.g., a polyether represented by the following formula:

wherein n is an integer of 2�n�10, R1 to R26 are a substituent having at least one element selected from carbon,hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, arbitrary R1 to R26, preferably R1 to R2n,may form a ring other than a benzene ring in cooperation, and the main chain may contain an atom other than carbon.[0074] Examples of such polyether compounds include2-(2-ethylhexyl)-1,3-dimethoxypropane,2-isopropyl-1,3-dimethoxypropane,2-butyl-1,3-dimethoxypropane,2-s-butyl-1,3-dimethoxypropane,2-cyclohexyl-1,3-dimethoxypropane,2-phenyl-1,3-dimethoxypropane,2-cumyl-1,3-dimethoxypropane,2-(2-phenylethyl)-1,3-dimethoxypropane,2-(2-cyclohexylethyl)-1,3-dimethoxypropane,2-(p-chlorophenyl)-1,3-dimethoxypropane,2-(diphenylmethyl)-1,3-dimethoxypropane,2-(1-naphthyl)-1,3-dimethoxypropane,2-(2-fluorophenyl)-1,3-dimethoxypropane,2-(1-decahydronaphthyl)-1,3-dimethoxypropane,2-(p-t-butylphenyl)-1,3-dimethoxypropane,2,2-dicyclohexyl-1,3-dimethoxypropane,

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2,2-diethyl-1,3-dimethoxypropane,2,2-dipropyl-1,3-dimethoxypropane,2,2-dibutyl-1,3-dimethoxypropane,2-methyl-2-propyl-1,3-dimethoxypropane,2-methyl-2-benzyl-1,3-dimethoxypropane,2-methyl-2-ethyl-1,3-dimethoxypropane,2-methyl-2-isopropyl-1,3-dimethoxypropane,2-methyl-2-phenyl-1,3-dimethoxypropane,2-methyl-2-cyclohexyl-1,3-dimethoxypropane,2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane,2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane,2-methyl-2-isobutyl-1,3-dimethoxypropane,2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane,2,2-diisobutyl-1,3-dimethoxypropane,2,2-diphenyl-1,3-dimethoxypropane,2,2-dibenzyl-1,3-dimethoxypropane,2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,2,2-diisobutyl-1,3-diethoxypropane,2,2-diisobutyl-1,3-dibutoxypropane,2-isobutyl-2-isopropyl-1,3-dimethoxypropane,2,2-di-s-butyl-1,3-dimethoxypropane,2,2-di-t-butyl-1,3-dimethoxypropane,2,2-dineopentyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,2-phenyl-2-benzyl-1,3-dimethoxypropane,2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane,2,3-diphenyl-1,4-diethoxybutane,2,3-dicyclohexyl-1,4-diethoxybutane,2,2-dibenzyl-1,4-diethoxybutane,2,3-diisopropyl-1,4-diethoxybutane,2,2-bis(p-methylphenyl)-1,4-dimethoxybutane,2,3-bis(p-chlorophenyl)-1,4-dimethoxybutane,2,3-bis(p-fluorophenyl)-1,4-dimethoxybutane,2,4-diphenyl-1,5-dimethoxypentane,2,5-diphenyl-1,5-dimethoxyhexane,2,4-diisopropyl-1,5-dimethoxypentane,2,4-diisobutyl-1,5-dimethoxypentane,2,4-diisoamyl-1,5-dimethoxypentane,3-methoxymethyltetrahydrofuran,3-methoxymethyldioxane,1,2-diisobutoxypropane,1,2-diisobutoxyethane,1,3-diisoamyloxyethane,1,3-diisoamyloxypropane,1,3-diisoneopentyloxyethane,1,3-dineopentyloxypropane,2,2-tetramethylene-1,3-dimethoxypropane,2,2-pentamethylene-1,3-dimethoxypropane,2,2-hexamethylene-1,3-dimethoxypropane,1,2-bis(methoxymethyl)cyclohexane,2,8-dioxaspiro[5,5]undecane,3,7-dioxabicyclo[3,3,1]nonane,3,7-dioxabicyclo[3,3,0]octane,3,3-diisobutyl-1,5-oxononane,6,6-diisobutyldioxyheptane,1,1-dimethoxymethylcyclopentane,1,1-bis(dimethoxymethyl)cyclohexane,1,1-bis(methoxymethyl)bicyclo[2,2,1]heptane,

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1,1-dimethoxymethylcyclopentane,2-methyl-2-methoxymethyl-1,3-dimethoxypropane,2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane,2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane,2,2-diisobutyl-1,3-dimethoxycyclohexane,2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane,2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane,2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane,2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane,2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane,2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,2-isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane,2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane and2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane.[0075] Also available as the polyethers are tris(p-methoxyphenyl)phosphine,methylphenylbis(methoxymethyl)silane,diphenylbis(methoxymethyl)silane,methylcyclohexylbis(methoxymethyl)silane,di-t-butylbis(methoxymethyl)silane,cyclohexyl-t-butylbis(methoxymethyl)silane,i-propyl-t-butylbis(methoxymethyl)silane or the like.[0076] Of these, 2,2-diisobutyl-1,3-dimethoxypropane,2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,2,2-dicyclohexyl-1,3-dimethoxypropane and2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane are preferably employed.[0077] As the electron donors (ii), organic acid esters and polyethers are preferable, and aromatic diesters, such asphthalic acid diesters, and polyethers are more preferable. The electron donors mentioned above can be used in com-bination of two or more kinds. The electron donors exemplified above have only to be finally contained in the solid titaniumcatalyst component (I). In the preparation of the solid titanium catalyst component (I), therefore, the above compoundsare not always used as such, and other compounds capable of producing the above compounds in the course of thepreparation of the solid titanium catalyst component (I) may be used. Also in this case, other compounds can be usedso as to produce two or more kinds of the electron donors (ii).

Preparation of solid titanium catalyst component (I)

[0078] The process for preparing the solid titanium catalyst component (I) from the aforesaid compounds is not spe-cifically restricted, and for example, the following processes are available. As the organometallic compound in thefollowing processes, the same compound as the later-described organometallic compound (II) is used.

(1) A liquid magnesium compound consisting essentially of the magnesium compound, the electron donor (i) andthe hydrocarbon solvent is contacted with a liquid titanium compound, after or with precipitating a solid by contactingthe liquid magnesium compound with an organometallic compound if necessary, and the resulting solid componentis contacted with an aromatic hydrocarbon, a liquid titanium compound and an electron donor (ii) at least once. It ispreferable to carry out the contact of the solid component with the aromatic hydrocarbon and the liquid titaniumcompound plural times.(2) A contact product of an inorganic carrier or an organic carrier with a liquid organomagnesium compound iscontacted with a liquid titanium compound, after or with precipitating a solid by contacting the contact product withan organometallic compound if necessary, and the resulting solid component is contacted with an aromatic hydro-carbon, a liquid titanium compound and an electron donor (ii) at least once. In this process, the contact product maybe previously contacted with a halogen-containing compound and/or an organometallic compound. It is preferableto carry out the contact of the solid component with the aromatic hydrocarbon and the liquid titanium compoundplural times.

(II) Organometallic compound catalyst component

[0079] The organometallic compound catalyst component (II) is preferably one containing a metal selected from Group

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13 of the periodic table, and preferred examples thereof include an organoaluminum compound, an organoboron com-pound and an alkyl complex compound of a Group 1 element and aluminum or boron. The organoaluminum compoundis, for example, an organoaluminum compound represented by the following formula:

RanAlX3-n

wherein Ra is a hydrocarbon group of 1 to 12 carbon atoms, X is a halogen or hydrogen, n is 1 to 3.[0080] Ra is a hydrocarbon group of 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group.Specific examples of such groups include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl,cyclohexyl, phenyl and tolyl.[0081] Examples of the organoaluminum compounds include:

trialkylaluminums, such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, triocty-laluminum and tri-2-ethylhexylaluminum;trialkenylaluminums, such as triisoprenylaluminum;dialkylaluminum halides, such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chlo-ride, diisobutylaluminum chloride and dimethylaluminum bromide;alkylaluminum sesquihalides, such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropyla-luminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide;alkylaluminum dihalides, such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichlo-ride and ethylaluminum dibromide; andalkylaluminum hydrides, such as diethylaluminum hydride, diisobutylaluminum hydride and ethylaluminum dihydride.

[0082] Also employable as the organoaluminum compound is a compound represented by the following formula.

RanAlY3-n

[0083] In the above formula, Ra is the same as described above, Y is -ORb, -OSiRc3, -OARd

2, -NRe2, -SiRf

3 or -N(Rg)AlRh

2, and n is 1 to 2.[0084] Rb, Rc, Rd and Rh are methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl or the like, Re is hydrogen, methyl,ethyl, isopropyl, phenyl, trimethylsilyl or the like, and Rf and Rg are methyl, ethyl or the like.[0085] Examples of such organoaluminum compounds include the following compounds:

(i) compounds represented by RanAl(ORb)3-n, such as dimethylaluminum methoxide, diethylaluminum ethoxide and

diisobutylaluminum methoxide;(ii) compounds represented by Ra

nAl(OSiRc)3-n, such as Et2Al(OSiMe3), (iso-Bu)2Al(OSiMe3) and (iso-Bu)2Al(OSiEt3) ;(iii) compounds represented by Ra

nAl(OAlRd2)3-n, such as Et2AlOAlEt2 and (iso-Bu)2AlOAl(iso-Bu)2;

(iv) compounds represented by RanAl(NRe

2)3-n, such as Me2AlNEt2, Et2AlNHMe, Me2AlNHEt, Et2AlN(Me3Si)2 and(iso-Bu)2AlN(Me3Si)2;(v) compounds represented by Ra

nAl(SiRf3)3-n, such as (iso-Bu)2AlSiMe3; and

(vi) compounds represented by RanAl[N(Rg)-AlRh

2]3-n, such as Et2AlN(Me)-AlEt2 and (iso-Bu)2AlN(Et)Al(iso-Bu)2.

[0086] Also available are compounds analogous to the above compounds, such as organoaluminum compoundswherein two or more aluminum atoms are bonded through an oxygen atom or a nitrogen atom. Examples of suchcompounds include (C2H5)2AlOAl(C2H5)2, (C4H9)2AlOAl(C4H9)2 and (C2H5)2AlN (C2H5)Al(C2H5)2. Aluminoxanes (or-ganoaluminum oxy-compounds), such as methylaluminoxane, are also available.[0087] An organoaluminum compound represented by the following formula is also employable.

RaAlXY

wherein Ra, X and Y are the same as described above.[0088] Examples of the organoboron compounds include triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluoroph-enyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, tris(3,5-dimethylphenyl)boron, hexylborane, dicyclohexylborane, diamylborane, diisopinocamphenylborane, 9-borabicyclo[3.3.1]nonane, catechol borane, B-bromo-9-borabicyclo[3.3.1]nonane, borane-triethylamine complex and borane-methylsulfide complex.[0089] An ionic compound may be used as the organoboron compound. Examples of such compounds include tri-

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ethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, trimethylammoniumtetra (p-tolyl) boron, tri-methylammoniumtetra(o-tolyl)boron, tri(n-butyl)ammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra(p-trifluoromethylphenyl)boron, N,N-dimethylaniliniumtetra(phenyl)bo-ron, dicyclohexylammoniumtetra(phenyl)boron, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, N,N-dimethyl-aniliniumtetrakis(pentafluorophenyl)borate, bis[tri(n-butyl)ammonium]nonaborate and bis[tri(n-butyl)ammonium]decab-orate.[0090] The alkyl complex compound of a Group 1 element and aluminum is, for example, a compound representedby the following formula:

M1AlRj4

wherein M1 is Li, Na or K, and Rj is a hydrocarbon group of 1 to 15 carbon atoms.[0091] Examples of such compounds include LiAl(C2H5)4 and LiAl (C7H15)4.[0092] Examples of the organoboron compounds and the alkyl complex compounds of a Group 1 element and boroninclude compounds having a structure wherein aluminum is replaced with boron in the aforesaid organoaluminum com-pounds and in the alkyl complex compounds of a Group 1 element and aluminum, respectively.

(III) Electron donor

[0093] As the electron donor (III), the compound previously exemplified as the electron donor (ii) that is used forpreparing the solid titanium catalyst component (I) is employable, and an organosilicon compound represented by thefollowing formula is also employable.

RnSi(OR’)4-n

wherein R and R’ are hydrocarbon groups, and 0<n<4.[0094] Examples of the organosilicon compounds represented by the above formula include trimethylmethoxysilane,trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, tert-butylmethyld-imethoxysilane, t-butylmethyldiethoxysilane, tert-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyld-imethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysi-lane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimeth-oxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltri-methoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloro-propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, tert-butyltriethoxysilane, n-butyl-triethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane,ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetri-methoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimeth-ylphenoxysilane, methyltriallyloxysilane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydis-iloxane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cy-clopentyltriethoxysilane, dicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcy-clopentyl)dimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicy-clopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethox-ysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane and cyclopentyldimethylethoxysilane.[0095] Of these, preferably used are ethyltriethoxysilane, n-propyltriethoxysilane, tert-butyltriethoxysilane, vinyltri-ethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane,2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysi-lane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane and cyclopentyldimethylmethox-ysilane.[0096] Also employable as the electron donors (III) are nitrogen-containing electron donors, such as 2,6-substitutedpiperidines, 2,5-substituted piperidines, substituted methylenediamines, specifically N,N,N’,N’-tetramethylmethylenedi-amine and N,N,N’,N’-tetraethylmethylenediamine, and substituted imidazolidines, specifically 1,3-dibenzylimidazolidineand 1,3-dibenzyl-2-phenylimidazolidine; phosphorus-containing electron donors, such as phosphates, specifically triethylphosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, diethyl-n-butyl phos-phite and diethylphenyl phosphite; and oxygen-containing electron donors, such as 2,6-substituted tetrahydropyransand 2,5-substituted tetrahydropyrans. The electron donors (III) mentioned above can be used in combination of two ormore kinds.

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Metallocene catalyst

[0097] The metallocene catalyst is described.[0098] There is no specific limitation on the metallocene catalyst for use in the preparation of the unmodified polyolefin,and a metallocene catalyst publicly known is employable. Examples of the publicly known metallocene catalysts includecompounds of transition metals such as titanium, vanadium, chromium, zirconium and hafnium, and any of the com-pounds, which are liquid or solid under the use conditions, can be employed. The transition metal compound does notneed to be a single compound, and the compound may be supported on another compound or may be a homogeneousmixture with another compound or may be a complex compound or a double compound with another compound.[0099] Of the publicly known metallocene catalysts, a metallocene compound of a chiral structure having C2 symmetryor C1 symmetry is preferably employed.[0100] Examples of the metallocene compounds of a chiral structure having C2 symmetry include rac-ethylene-bis(indenyl)zirconium dichloride, rac-ethylene-bis(tetrahydroindenyl)zirconium dichloride, rac-dimethylsilyl-bis(2,3,5-tri-methylcyclopentadienyl) zirconium dichloride, rac-dimethylsilyl-bis[1-(4-phenylindenyl)]zirconium dichloride, rac-dimeth-ylsilyl-bis[1-(2-methyl-4-phenylindenyl)] zirconium dichloride, rac-dimethylsilyl-bis{1-[2-methyl-4-(1-naphthyl)indenyl]}zirconium dichloride, rac-dimethylsilyl-bis{1-[2-methyl-4-(2-naphthyl)indenyl]} zirconium dichloride, rac-dimethylsilyl-bis{1-[2-methyl-4-(1-anthryl)indenyl]} zirconium dichloride, rac-dimethylsilyl-bis{1-[2-methyl-4-(9-anthryl)indenyl]} zirconi-um dichloride, rac-dimethylsilyl-bis{1-[2-methyl-4-(9-phenanthryl) indenyl]}zirconium dichloride, rac-dimethylsilyl-bis{1-[2-methyl-4-(o-chlorophenyl) indenyl]}zirconium dichloride, rac-dimethylsilyl-bis{1-[2-methyl-4-(pentafluorophenyl) in-denyl]}zirconium dichloride, rac-dimethylsilyl-bis[1-(2-ethyl-4-phenylindenyl)] zirconium dichloride, rac-dimethylsilyl-bis{1-[2-ethyl-4-(1-naphthyl)indenyl]} zirconium dichloride, rac-dimethylsilyl-bis{1-[2-ethyl-4-(9-phenanthryl) indenyl]}zirco-nium dichloride, rac-dimethylsilyl-bis[1-(2-n-propyl-4-phenylindenyl)] zirconium dichloride, rac-dimethylsilyl-bis{1-[2-n-propyl-4-(1-naphthyl) indenyl]}zirconium dichloride and rac-dimethylsilyl-bis{1-[2-n-propyl-4-(9-phenanthryl) indenyl]}zir-conium dichloride. Of the compounds, metallocene compounds having bulky substituents, such as rac-dimethylsilyl-bis{1-[2-ethyl-4-(1-naphthyl)indenyl]} zirconium dichloride, rac-dimethylsilyl-bis{1-[2-ethyl-4-(9-phenanthryl) indenyl]}zirco-nium dichloride, rac-dimethylsilyl-bis{1-[2-n-propyl-4-(1-naphthyl) indenyl]}zirconium dichloride and rac-dimethylsilyl-bis{1-[2-n-propyl-4-(9-phenanthryl) indenyl]}zirconium dichloride, are more preferably employed.[0101] Examples of the metallocene compounds of a chiral structure having C1 symmetry include ethylene[2-methyl-4-(9-phenanthryl)-1-indenyl] (9-fluorenyl)zirconium dichloride, ethylene[2-methyl-4-(9-phenanthryl)-1-indenyl] (2,7-dimethyl-9-fluorenyl)zirconium dichloride, dimethylsilyl(9-fluorenyl)(3-t-butylcyclopentadienyl) zirconium dichloride anddiphenylsilyl(9-fluorenyl)(3-t-butylcyclopentadienyl) zirconium dichloride.[0102] The metallocene compounds mentioned above may be used singly or in combination of two or more kinds,and may be used in combination with the aforesaid solid titanium catalyst component (I).[0103] The metallocene compound is used in combination with the aforesaid organometallic catalyst component (II).[0104] One example of the metallocene catalyst is described below.[0105] The metallocene catalyst is formed from, for example,

(a) a transition metal compound of a Group 4 metal of the periodic table, which contains a ligand having a cyclopen-tadienyl skeleton, (sometimes referred to as "metallocene compound (a)" hereinafter),(b) an organoaluminum oxy-compound,and optionally(c) a particulate carrier.

(a) Metallocene compound

[0106] The metallocene compound (a) is represented by the following formula (1).

MLx (1)

[0107] - In the above formula, M is a transition metal atom of Group 4 of the periodic table, specifically zirconium,titanium or hafnium.[0108] L is a ligand coordinated to the transition metal atom. At least one of L is a ligand containing a ligand havinga cyclopentadienyl skeleton, and L other than the ligand containing a ligand having a cyclopentadienyl skeleton is ahydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a SO3R group (Ris a hydrocarbon group of 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen or hydrogen,x is a number satisfying a valence of the transition metal atom.[0109] Examples of the ligands containing a ligand having a cyclopentadienyl skeleton include a cyclopentadienylgroup; alkyl-substituted cyclopentadienyl groups, such as a methylcyclopentadienyl group, a dimethylcyclopentadienyl

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group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, a pentamethylcyclopentadienyl group,an ethylcyclopentadienyl group, a methylethylcyclopentadienyl group, a propylcyclopentadienyl group, a methylpropyl-cyclopentadienyl group, a butylcyclopentadienyl group, a methylbutylcyclopentadienyl group and a hexylcyclopentadienylgroup; an indenyl group; a 4,5,6,7-tetrahydroindenyl group; and a fluorenyl group. These groups may be substitutedwith a halogen, a trialkylsilyl group or the like.[0110] When the compound of the formula (I) contains two or more groups having a cyclopentadienyl skeleton, twoof the groups having a cyclopentadienyl skeleton may be bonded to each other through an alkylene group such asethylene or propylene, a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group, ora substituted silylene group such as dimethylsilylene, diphenylsilylene or methylphenylsilylene.[0111] The ligand L other than the ligand having a cyclopentadienyl skeleton is, for example, as follows. Examples ofthe hydrocarbon groups of 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups.[0112] More specifically, there can be mentioned:

alkyl groups, such as methyl, ethyl, propyl, isopropyl and butyl;cycloalkyl groups, such as cyclopentyl and cyclohexyl;aryl groups, such as phenyl and tolyl; andaralkyl groups, such as benzyl and neophyl.

[0113] Examples of the alkoxy groups include methoxy, ethoxy and butoxy.[0114] Examples of the aryloxy groups include phenoxy.[0115] Examples of the halogens include fluorine, chlorine, bromine and iodine.[0116] Examples of the ligands represented by SO3R include a p-toluenesulfonato group, a methanesulfonate groupand a trifluoromethanesulfonato group.[0117] When the valence of the transition metal atom is 4, the metallocene compound (a) containing a ligand havinga cyclopentadienyl skeleton is more specifically represented by the following formula (2):

R1aR2

bR3cR4

dM (2)

wherein M is the same transition metal atom as M in the formula (1), R1 is a group (ligand) having a cyclopentadienylskeleton, R2, R3 and R4 are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an arylgroup, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a SO3R group, a halogen or hydrogen,a is an integer of 1 or greater, and a+b+c+d=4.[0118] A metallocene compound wherein at least two of R1, R2, R3 and R4 in the formula (2), for example, R1 and R2,are groups (ligands) having a cyclopentadienyl skeleton is preferably employed.[0119] When the metallocene compound has two or more groups having a cyclopentadienyl skeleton, two of the groupshaving a cyclopentadienyl skeleton may be bonded through an alkylene group such as ethylene or propylene, a substitutedalkylene group such as isopropylidene or diphenylmethylene, a silylene group, or a substituted silylene group such asdimethylsilylene, diphenylsilylene or methylphenylsilylene.[0120] R3 and R4 are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group,an aralkyl group, an al koxy group, an aryloxy group, a trialkylsilyl group, a SO3R group, a halogen or hydrogen.[0121] Examples of the metallocene compounds wherein M is zirconium include bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dibromide, bis(indenyl)zirconiumbis(p-toluenesulfonato)bis(4,5,6,7-tetrahydroindenyl)zirconiumdichloride, bis(fluorenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconiumdibromide, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)methyl-zirconium monochloride, ethylenebis(indenyl)zirconiumbis(methanesulfonato), ethylenebis(indenyl)zirconiumbis(p-tol-uenesulfonato), ethylenebis(indenyl)zirconiumbis(trifluoromethanesulfonato), ethylenebis(4,5,6,7-tetrahydroindenyl)zir-conium dichloride, isopropylidene(cyclopentadienyl-fluorenyl)zirconium dichloride, isopropylidene(cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsi-lylenebis(methylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(dimethylcyclopentadienyl)zirconium dichlo-ride, dimethylsilylenebis(trimethylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(indenyl)zirconium dichlo-ride, dimethylsilylenebis(indenyl)zirconiumbis (trifluoromethanesulfonato), dimethylsilylenebis(4,5,6,7-tetrahydroinde-nyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl-fluorenyl)zirconium dichloride, diphenylsilylenebis(indenyl)zirconium dichloride, methylphenylsilylenebis(indenyl)zirconium dichloride, bis(cyclopentadienyl)zirconium dichloride,bis(cyclopentadienyl)zirconium dibromide, bis(cyclopentadienyl)methylzirconium monochloride, bis(cyclopentadienyl)ethylzirconium monochloride, bis(cyclopentadienyl)cyclohexylzirconium monochloride, bis(cyclopentadienyl)phenylzir-conium monochloride, bis(cyclopentadienyl)benzylzirconium monochloride, bis(cyclopentadienyl)zirconium monochlo-ride monohydride, bis(cyclopentadienyl)methylzirconium monohydride, bis(cyclopentadienyl)dimethylzirconium, bis(cy-clopentadienyl)diphenylzirconium, bis(cyclopentadienyl)dibenzylzirconium, bis(cyclopentadienyl)zirconium methoxy-

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chloride, bis(cyclopentadienyl)zirconium ethoxychloride, bis(cyclopentadienyl)zirconiumbis(methanesulfonato), bis(cy-clopentadienyl)zirconiumbis(p-toluenesulfonato), bis(cyclopentadienyl)zirconiumbis (trifluoromethanesulfonato), bis(methylcyclopentadienyl)zirconium dichloride, bis(dimethylcyclopentadienyl)zirconium dichloride, bis(dimethylcyclopen-tadienyl)zirconium ethoxychloride, bis(dimethylcyclopentadienyl)zirconiumbis (trifluoromethanesulfonato), bis(ethylcy-clopentadienyl)zirconium dichloride, bis(methylethylcyclopentadienyl)zirconium dichloride, bis(propylcyclopentadienyl)zirconium dichloride, bis(methylpropylcyclopentadienyl)zirconium dichloride, bis(butylcyclopentadienyl)zirconiumdichloride, bis(methylbutylcyclopentadienyl)zirconium dichloride, bis(methylbutylcyclopentadienyl)zirconiumbis (meth-anesulfonato), bis(trimethylcyclopentadienyl)zirconium dichloride, bis(tetramethylcyclopentadienyl)zirconium dichloride,bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(hexylcyclopentadienyl)zirconium dichloride and bis(trimeth-ylsilylcyclopentadienyl)zirconium dichloride.[0122] In the above examples, the di-substitution products of cyclopentadienyl rings include 1,2- and 1,3-substitutionproducts, and the tri-substitution products of cyclopentadienyl rings include 1,2,3- and 1,2,4-substitution products. Thealkyl groups such as propyl and butyl include isomers such as n-, iso-, sec- and tert-groups.[0123] Compounds wherein zirconium is replaced with titanium or hafnium in the above-mentioned zirconium com-pounds are also employable as the metallocene compounds (a).[0124] These compounds may be used singly or in combination of two or more kinds. These compounds may be used,diluting with a hydrocarbon or a halogenated hydrocarbon.[0125] As the metallocene compound (a), a zirconocene compound having zirconium as the central metal atom andhaving at least two ligands containing a cyclopentadienyl skeleton is preferably employed.

(b) Organoaluminum oxy-compound

[0126] The organoaluminum oxy-compound (b) is, for example, a hitherto known aluminoxane or a benzene-insolublealuminum oxy-compound as disclosed in Japanese Patent Laid-Open Publication No. 276807/1990.[0127] The hitherto known aluminoxane can be prepared from the later-described organoaluminum compound (b-2)by, for example, the following processes.

(1) An organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of acompound containing adsorption water or a salt containing water of crystallization, e.g., magnesium chloride hydrate,copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, to performreaction, and the aluminoxane is recovered as a solution in the hydrocarbon.(2) Water (water, iceorwatervapor) isallowedtodirectly act on an organoaluminum compound such as trialkylalumi-num in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran, and the aluminoxane is recovered as asolution in the above medium.(3) An organotin oxide such as dimethyltin oxide or dibutyltin oxide is allowed to react with an organoaluminumcompound such as trialkylaluminum in a medium such as decane, benzene or toluene.

[0128] It is possible that the solvent or the unreacted organoaluminum compound is removed from the recoveredsolution of aluminoxane by distillation and the remainder is redissolved in a solvent.[0129] The organoaluminum oxy-compound (b) may contain a small amount of a metallic component other thanaluminum.

(c) Particulate carrier

[0130] Examples of the particulate carriers (c) optionally used include inorganic carriers, such as SiO2, Al2O3, B2O3,MgO, ZrO2, CaO, TiO2, ZnO, Zn2O, SnO2, BaO and ThO; and resins (organic carriers), such as polyethylene, polypro-pylene, poly-1-butene, poly-4-methyl-1-pentene and a styrene/divinylbenzene copolymer. Of these, SiO2 is preferable.These carriers can be used in combination of two or more kinds.

Preparation of metallocene catalyst

[0131] When the metallocene catalyst is a solid metallocene catalyst consisting essentially of the metallocene com-pound (a), the organoaluminum oxy-compound (b) and the particulate carrier (c), this solid metallocene catalyst is formedby supporting the metallocene compound (a) and the organoaluminum oxy-compound (b) on the particulate carrier (c)in accordance with a hitherto known method.[0132] The solid metallocene catalyst may be formed by supporting the later-described organoaluminum compound(b-2) together with the metallocene compound (a) and the organoaluminum oxy-compound (b) on the particulate carrier.[0133] In the preparation of the solid metallocene catalyst, the metallocene compound (a) is used in an amount in

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terms of a transition metal atom of usually 0.001 to 1.0 mmol, preferably 0.01 to 0.5 mmol, based on 1 g of the particulatecarrier (c), and the organoaluminum oxy-compound (b) is used in an amount of usually 0.1 to 100 mmol, preferably 0.5to 20 mmol.[0134] The solid metallocene catalyst has a particle diameter of usually 1 to 300 Pm, preferably 10 to 100 Pm.[0135] The solid metallocene catalyst may contain, if necessary, other components useful for the olefin polymerization,such as an electron donor and a reaction assistant, together with the above-mentioned catalyst components.[0136] The solid metallocene catalyst for use in the invention may be a prepolymerized catalyst obtained by prepo-lymerizing an olefin onto the solid metallocene catalyst.[0137] When the olefin polymerization is carried out using the metallocene catalyst, the following organoaluminumcompound (b-2) can be used together with the metallocene catalyst.

(b-2) Organoaluminum compound

[0138] Examples of the organoaluminum compounds (b-2), which are used as the organoaluminum compounds (b-2) for the olefin polymerization and used for preparing the aforesaid solution of the organoaluminum oxy-compound (b),include:

trialkylaluminums, such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-buty-laluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum,trioctylaluminum, tridecylaluminum, tricyclohexylaluminum and tricyclooctylaluminum;dialkylaluminum halides, such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromideand diisobutylaluminum chloride;dialkylaluminum hydrides, such as diethylaluminum hydride and diisobutylaluminum hydride;dialkylaluminum alkoxides, such as dimethylaluminum methoxide and diethylaluminum ethoxide; anddialkylaluminum aryloxides, such as diethylaluminum phenoxide.

[0139] Of these, trialkylaluminums are preferable, and triethylaluminum and triisobutylaluminum are particularly pref-erable.[0140] Also employable as the organoaluminum compound is isoprenylaluminum represented by the following formula:

(i-C4H9)xAly(C5H10)z

wherein x, y and z are positive integers, and zA2x.[0141] These organoaluminum compounds may be used in combination of two or more kinds.[0142] The organoaluminum compound (b-2) may contain a small amount of a metallic component other than aluminum.[0143] When the organoaluminum compound (b-2) is supported on the particulate carrier (c) together with the metal-locene compound (a) and the organoaluminum oxy-compound (b), the organoaluminum compound (b-2) is used in anamount of usually 1 to 300 mol, preferably 2 to 200 mol, based on 1 mol (in terms of a transition metal atom) of the solidmetallocene catalyst.

Preparation of unmodified polyolefin

[0144] In the present invention, an olefin of 2 to 20 carbon atoms is polymerized or copolymerized in the presence ofthe catalyst mentioned above to prepare an unmodified polyolefin.[0145] Examples of the olefins of 2 to 20 carbon atoms preferably used include ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene and 4-methyl-1-pentene. These monomers may be used singly or in combinationof two or more kinds, or may be copolymerized with polymerizable monomers such as dienes other than olefins.[0146] When the monomers are used singly, propylene is particularly preferable. When the monomers are used incombination of two or more kinds, combinations of ethylene and propylene; ethylene and butene; ethylene and octane;ethylene, propylene and butene; and ethylene, propylene and diene are preferable.[0147] The olefin polymerization can be carried out by any of liquid phase polymerization, such as solution polymer-ization and suspension polymerization, and gas phase polymerization. As the polymerization reaction type, suspensionpolymerization is preferably adopted. As the reaction solvent for the suspension polymerization, an inert hydrocarbonsolvent may be used, or an olefin that is liquid at the reaction temperature may be used.[0148] Examples of the inert hydrocarbon media employable in the suspension polymerization include aliphatic hy-drocarbons, such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosine; alicyclichydrocarbons, such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons, such as benzene,toluene and xylene; halogenated hydrocarbons, such as ethylene chloride and chlorobenzene; and combinations of

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these hydrocarbons. Of these, aliphatic hydrocarbons are particularly preferably employed.[0149] When the unmodified polyolefin is prepared by the use of the magnesium-supported titanium catalyst systemas a catalyst, the solid titanium catalyst component (I) or its prepolymerized catalyst is used in an amount of usuallyabout 0.001 to 100 mmol, preferably about 0.005 to 20 mmol, in terms of titanium atom, based on 1 liter of the polym-erization volume. The organometallic compound catalyst component (II) is used in an amount of the metal atom in thecatalyst component (II) of usually about 1 to 2000 mol, preferably about 2 to 500 mol, based on 1 mol of the titaniumatom in the solid titanium catalyst component (I) in the polymerization system. The electron donor (III) is used in anamount of usually 0.001 to 10 mol, preferably0.01 to 5 mol, based on 1 mol of the metal atom in the organometallic compound catalyst component (II).[0150] In the polymerization process, the amount of hydrogen is in the range of usually 0 to 0.25 mol, preferably 0 to0.20 mol, more preferably 0 to 0.15 mol, based on 1 mol of the monomer.[0151] When the magnesium-supported titanium catalyst system is used, the polymerization temperature is in therange of usually about 20 to 300°C, preferably about 50 to 150°C, and the polymerization pressure is in the range of0.01 to 10 MPa, preferably 0.05 to 5 MPa.[0152] When the unmodified polyolefin is prepared by the use of the metallocene catalyst as a catalyst, the amountof the metallocene compound (a) used in the polymerization system is in the range of usually 0.00005 to 0.1 mmol,preferably 0.0001 to 0.05 mmol, based on 1 liter of the polymerization volume. The organoaluminum oxy-compound (b)is used in such an amount that the molar ratio (Al/M) of the aluminum atom (Al) to the transition metal atom (M) in themetallocene compound (a) becomes 5 to 1000, preferably 10 to 400. If the organoaluminum compound (b-2) is used,the organoaluminum compound (b-2) is used in an amount of usually about 1 to 300 mol, preferably about 2 to 200 mol,based on 1 mol of the transition metal atom in the metallocene compound (a).[0153] When the metallocene catalyst is used, the polymeri zation temperature is in the range of usually -20 to 150°C,preferably 0 to 120°C, more preferably 0 to 100°C, and the polymerization pressure is higher than 0 MPa and not higherthan 8 MPa, preferably higher than 0 MPa and not higher than 5 MPa.[0154] The olefin polymerization can be carried out by any of batchwise, semi-continuous and continuous processes.The polymerization can be carried out in two or more steps under different reaction conditions. In the olefin polymerization,a homopolymer of an olefin may be prepared, or a random copolymer may be prepared from two or more kinds of olefins.[0155] For preparing a branched polyolefin wherein the composition of the olefin chain (A) is the same as that of theolefin chain (B), the unmodified polyolefin to be prepared in the olefin polymerization is preferably polypropylene, andthis polypropylene desirably has a density of 0.880 to 0.960 g/cm3, particularly 0.890 to 0.950 g/cm3, and MFR of 0.05to 1,000 g/10 min, particularly 0.1 to 500 g/10 min. When the polypropylene is a copolymer, the amount of the copoly-merized component is desired to be usually not more than 10 % by mol, particularly not more than 5 % by mol.[0156] For preparing a branched polyolefin wherein the composition of the olefin chain (A) is different from that of theolefin chain (B), the unmodified polyolefin to be prepared in the olefin polymerization is preferably a copolymer of ethyleneand an olefin of 3 to 20 carbon atoms, and this copolymer has a density of 0.850 to 0.900 g/cm3, preferably 0.858 to0.898 g/cm3, more preferably 0.855 to 0.895 g/cm3, MFR of 0.1 to 50 g/10 min, preferably 0.2 to 40 g/10 min, morepreferably 0.3 to 30 g/10 min, and a crystallinity, as measured by X-rays, of less than 30 %, preferably less than 28 %,more preferably less than 25 %.

Modification of unmodified polyolefin

[0157] The functional group-containing polyolefin is obtained by graft modifying a part or the whole of the unmodifiedpolyolefin with a graft monomer which is maleic acid or its derivatives. In order to prepare the functional group-containingpolyolefin through graft copolymerization of the unmodified polyolefin with a graft monomer selected from the unsaturatedcarboxylic acids and their derivatives, various processes hitherto known are adoptable.[0158] For example, there are a process comprising melting the unmodified polyolefin and adding a graft monomerto perform graft copolymerization, and a process comprising dissolving the unmodified polyolefin in a solvent and addinga graft monomer to perform graft copolymerization. In either process, it is preferable to carry out the reaction in thepresence of a radical initiator in order to efficiently graft copolymerize the graft monomer.[0159] The graft copolymerization is carried out at a temperature of usually 60 to 350°C. The radical initiator is usedin an amount of usually 0.001 to 1 part by weight based on 100 parts by weight of the unmodified polyolefin.[0160] Examples of the radical initiators employable herein include organic peroxides and organic peresters. Specif-ically, there can be mentioned benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butylperoxide, 2,5-dimethyl-2,5-di(peroxybenzoate)hexyne-3, 1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl pera-cetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl perben-zoate, tert-butylperphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl per-pivalate and tert-butylperdiethyl acetate. Also employable are azo compounds, such as azobisisobutyronitrile and dime-thyl azoisobutyrate. Of these, preferable are dialkyl peroxides, such as dicumyl peroxide, di-tert-butyl peroxide, 2, 5-

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dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2, 5-dimethyl-2,5-di(tert-butylperoxy)hexane and 1,4-bis(tert-butylperoxyiso-propyl) benzene.[0161] In the functional group-containing polyolefin (C) obtained above, the graft quantity of the unsaturated carboxylicacid or its derivative is in the range of 0.05 to 15 % by weight, preferably 0.08 to 13 % by weight, more preferably 0.1to 10 % by weight, based on the amount of the unmodified polyolefin.[0162] When the functional group-containing polyolefin (C) is a polyolefin obtained by modifying an ethylene (co)polymer, this polyolefin desirably has MFR of usually 0.001 to 1,000 g/10 min, preferably 0.005 to 500 g/10 min, morepreferably 0.01 to 100 g/10 min, and a density of usually 0.70 to 1.0 g/cm3, preferably 0.75 to 0.98 g/cm3, more preferably0.80 to 0.96 g/cm3. This functional group-containing polyolefin (C) is preferably used for the preparation of a branchedpolyolefinwherein the composition of the olefin chain (A) is different from that of the olefin chain (B).[0163] When the functional group-containing polyolefin (C) is a polyolefin obtained by modifying a propylene (co)polymer, this polyolefin desirably has MFR of usually 0.05 to 1,000 g/10 min, preferably 0.1 to 500 g/10 min, morepreferably 0.2 to 300 g/10 min, and a density of usually 0.880 to 0. 960 g/cm3, preferably 0.890 to 0.950 g/cm3, morepreferably 0. 900 to 0.940 g/cm3. This functional group-containing polyolefin (C) is preferably used for the preparationof a branched polyolefin wherein the composition of the olefin chain (A) is the same as that of the olefin chain (B).

(D) Terminal modified polyolefin

[0164] The terminal modified polyolefin (D) is a polyolefin having an olefin composition which is the same as or differentfrom that of the functional group-containing olefin polymer (C) and containing at least one group capable of reacting witha carboxyl group or an acid anhydride group at only the position of chain end. The terminal modified polyolefin is preferablya polyolefin having a group capable of reacting with a carboxyl group or an acid anhydride group at only one-side-end.The terminal modified polyolefin (D) becomes the olefin chain (B), and the group capable of reacting with a carboxylgroup or an acid anhydride group becomes a bond having a carbonyl group for linking the olefin chain (A) to the olefinchain (B).[0165] Examples of the groups capable of reacting with a carboxyl group or an acid anhydride group include a hydroxylgroup, an alkoxy group, an amino group, an imino group and a halogen. Of these, a hydroxyl group and an amino groupare preferable.[0166] The terminal modified polyolefin (D) can be prepared by, for example, a process comprising preparing a poly-olefin having a Group 13 element-containing group represented by -AlR1R2 at an end (said polyolefin being sometimesreferred to as a "Group 13 element containing group-containing polyolefin" hereinafter), and then conducting substitutionreaction of the Group 13 element-containing group of the Group 13 element containing group-containing polyolefin witha compound having a functional group structure, or conducting reaction of the Group 13 element-containing group ofthe Group 13 element containing group-containing polyolefin with a compound having a structure that forms a functionalgroup by solvolysis, followed by conducting solvolysis. The resulting terminal functional group may be converted intoanother functional group through the later-described reaction.[0167] The terminal modified polyolefin (D) can be prepared by polymerizing or copolymerizing an olefin of 2 to 20carbon atoms using, for example, the above-mentioned magnesium-supported titanium catalyst system or metallocenecatalyst.[0168] Examples of the olefins of 2 to 20 carbon atoms preferably used include ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene and 4-methyl-1-pentene. Of these, ethylene and/or propylene are more preferablyemployed, and propylene is most preferably employed.[0169] When the magnesium-supported titanium catalyst system is used, the solid titanium catalyst component (I) orits prepolymerized catalyst is used in the polymerization system in an amount of usually about 0.0001 to 50 mmol,preferably about 0.001 to 10 mmol, in terms of the titanium atom, based on 1 liter of the polymerization volume. Theorganometallic compound catalyst component (II) is used in an amount of the metal atom in the catalyst component (II)of usually 1 to 2000 mol, preferably 2 to 1000 mol, based on 1 mol of the titanium atom in the solid titanium catalystcomponent (I) in the polymerization system. If the electron donor (III) is used, this electron donor (III) is used in an amountof usually 0.001 to 10 mol, preferably 0.01 to 5 mol, based on 1 mol of the metal atom in the organometallic compoundcatalyst component (II).[0170] When the metallocene catalyst is used as a catalyst for polymerization, the amount of the metallocene compound(a) in the polymerization system is in the range of usually 0.00005 to 0.1 mmol, preferably 0.0001 to 0.05 mmol, basedon 1 liter of the polymerization volume. If the organoaluminum oxy-compound (b) is used, this compound (b) is used insuch an amount that the molar ratio (Al/M) of the aluminum atom (Al) to the transition metal atom (M) in the metallocenecompound (a) becomes 5 to 1000, preferably 10 to 400. If the organoaluminum compound (b-2) is used, this compound(b-2) is used in an amount of usually about 1 to 300 mol, preferably about 2 to 200 mol, based on 1 mol of the transitionmetal atom in the metallocene compound (a).

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[0171] The olefin polymerization can be carried out by any of liquid phase polymerization, such as solution polymer-ization and suspension polymerization, and gas phase polymerization. As the reaction solvent for the suspension po-lymerization, the aforesaid inert hydrocarbon solvent may be used, or an olefin that is liquid at the reaction temperaturemay be used. The reaction temperature is in the range of usually -50 to 200°C, preferably 0 to 150°C, and the polym-erization pressure is in the range of usually 0.01 to 10 MPa, preferably 0.1 to 5 MPa. The olefin polymerization can becarried out by any of batchwise, semi-continuous and continuous processes. When the olefin polymerization is conductedin two or more steps, the reaction conditions may be the same or different.[0172] It is preferable that molecular hydrogen that is a general molecular weight modifier is not present in the olefinpolymerization, and regulation of the molecular weight is preferably carried out by controlling one or more conditionsselected from the concentration of the organometallic catalyst component (II), the polymerization temperature and theconcentration (polymerization pressure) of the olefin. The molecular weight is specifically regulated as follows. Forexample, in the suspension polymerization wherein molecular hydrogen is not present substantially, the concentrationof the organometallic catalyst component (II) is increased, whereby the molecular weight of the resulting polyolefin canbe decreased, or in the suspension polymerization wherein molecular hydrogen is not present substantially, the polym-erization temperature is increased, whereby the molecular weight of the resulting polyolefin can be decreased.[0173] The polyolefin obtained as above has a Group 13 element-containing group and/or an unsaturated bond at anend, preferably at only one-side-end. Whether the end of the polyolefin is a Group 13 element-containing group or anunsaturated bond depends upon the polymerization conditions, such as the type of the catalyst used, the type and/orthe amount of the organometallic catalyst component, and the polymerization temperature.[0174] When the end of the polyolefin is an unsaturated bond, the unsaturated bond can be converted into a Group13 element-containing group through the reaction with the compound containing the Group 13 element. For preparinga polyolefin having the unsaturated bond at an end, the aforesaid process using the metallocene catalyst is preferable.Further, the polyolefin having the unsaturated bond(s) at end(s) can be prepared also by thermally decomposing apolyolefin having neither a Group 13 element-containing group nor an unsaturated bond at an end that is prepared bya conventional process, and the resulting polyolefin can be preferably employed. Also when the resulting polyolefin isa mixture of a polyolefin wherein a Group 13 element is bonded to an end and a polyolefin having an unsaturated bondat an end, the terminal unsaturated bond of the polyolefin may be converted into an end to which a Group 13 elementis bonded if necessary.[0175] The compound containing a Group 13 element, which is used for the reaction, is selected from the aforesaidcompounds exemplified as the organometallic compound catalyst components (II). Of such compounds, those exem-plified as the organoaluminum compounds or the organoboron compounds are preferably employed. Of these, trialky-laluminum, dialkylaluminum hydride or a boron compound having one or more hydrogen-boron bonds is more preferable.[0176] The reaction of the polyolefin having unsaturated bond (s) at end(s) with the compound containing Group 13element(s) is carried out by, for example, the following processes.

(1) Polypropylene having a vinylidene group at an end, in an amount of 0.1 to 50 g, is mixed with 5 to 1000 ml ofan octane solution of diisobutylaluminum hydride having a concentration of 0.01 to 5 mol/l, and the mixture wasrefluxed for 0.5 to 6 hours.(2) Polypropylene having a vinylidene group at an end, in an amount of 0.1 to 50 g, is mixed with 5 to 1000 ml ofanhydrous tetrahydrofuran and 0.1 to 50 ml of a tetrahydrofuran solution of 9-borabicyclo[3.3.1]nonane having aconcentration of 0.05 to 10 mol/l, and the mixture is stirred at 20 to 65°C for 0.5 to 24 hours.

[0177] Through the above processes, a terminal modified polyolefin is prepared. To the end of the resulting polyolefin,preferably to only one-side-end thereof, a Group 13 element is bonded, and the Group 13 element is preferably aluminum.[0178] The Group 13 element containing group-containing polyolefin prepared above is usually obtained as a slurry.[0179] Subsequently, (1) a substitution reaction of the Group 13 element-containing group of the Group 13 elementcontaining group-containing polyolefin with a compound having a functional group structure is carried out, or (2) a reactionof the Group 13 element-containing group of the Group 13 element containing group-containing polyolefin with a com-pound having a structure that forms a functional group by solvolysis is carried out, followed by solvolysis. Thus, a terminalmodified polyolefin is prepared. The resulting terminal functional group may be converted into another functional groupthrough the later-described reaction.[0180] Examples of the compounds having a functional group structure include a halogen, methyl chloroformate andphthaloyl chloride.[0181] Examples of the compounds having a structure that forms a functional group by solvolysis include oxygen,carbon monoxide and carbon dioxide.[0182] The substitution reaction of the Group 13 element-containing group of the Group 13 element containing group-containing polyolefin with the compound having a functional group structure or the compound having a structure thatforms a functional group by solvolysis is carried out at a temperature of usually 0 to 300°C, preferably 10 to 200°C, for

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0 to 100 hours, preferably 0.5 to 50 hours.[0183] The temperature for the solvolysis is in the range of usually 0 to 100°C, preferably 10 to 80°C, and the solvolysistime is in the range of 0 to 100 hours, preferably 0.5 to 50 hours.[0184] Examples of solvents used for the solvolysis include methanol, ethanol, propanol, butanol and water.[0185] The group with which the end is modified is a group capable of reacting with a carboxyl group or an acidanhydride group. Examples of such groups include a hydroxyl group, an alkoxy group, an amino group, an imino groupand a halogen. Of these, particularly preferable is a hydroxyl group, an amino group or a halogen.[0186] Examples of conversions of the end of the Group 13 element containing group-containing polyolefin having-AlR1R2 group at an end into a hydroxyl group, a halogen or an amino group are given below.

(1) Conversion into hydroxyl group

[0187] After contact with dried air, a large excess of methanol containing a small amount of hydrochloric acid is addedto a -AlR1R2 group-containing polyolefin, followed by stirring for 5 minutes to 12 hours.

(2) Conversion into halogen

[0188] To the polymer obtained by the above process (1), thionyl chloride of 1 to 10 times mol as much as the hydroxylgroup is added, followed by the reaction at 0 to 100°C for 5 minutes to 24 hours. Instead of thionyl chloride, thionylbromide is employable.

(3) Conversion into amino group.

[0189] To the polymer obtained by the above process (2), sodium azide of 1 to 10 times mol as much as the halogenis added, followed by the reaction at 50 to 150°C for 0.5 to 24 hours. To the resulting reaction product, triphenylphosphineof 1 to 10 times mol as much as the sodium azide is added, followed by the reaction at 0 to 100°C for 0.5 to 24 hours.[0190] Similarly to the polyolefin having a Group 13 element-containing group at an end, a polyolefin having a groupcontaining an element other than a Group 13 element at an end is also employable. The polyolefin having a groupcontaining an element other than a Group 13 element at an end is prepared by living polymerization or chain transferreaction hitherto known. In particular, a polyolefin having a group containing an element of 3, 4, 5 or 10 Group at anend, which is prepared by living polymerization, or a polyolefin having a group containing a Group 12 element or silicon(Si) at an end, which is prepared by chain transfer reaction, is preferable.[0191] The terminal modified polyolefin (D) obtained as above has MFR of usually 0.01 to 5,000 g/10 min, preferably0.05 to 3,000 g/10 min, more preferably 0.1 to 1,500 g/10 min, and a density of usually 0.7 to 1.0 g/cm3, preferably 0.75to 0.98 g/cm3, more preferably 0.80 to 0.96 g/cm3. The weight-average molecular weight (Mw) of the polyolefin is desiredto be in the range of usually not less than 5,000, preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000.[0192] When the branched polyolefin wherein the composition of the olefin chain (A) is the same as that of the olefinchain (B) is prepared, the terminalmodifiedpolyolefin (D) desirably has MFR of usually 0.01 to 3,000 g/10 min, preferably0.05 to 1,000 g/10 min, more preferably 0.1 to 500 g/10 min, and a density of usually 0.880 to 0.960 g/cm3, preferably0.890 to 0.950 g/cm3, more preferably 0.900 to 0.940 g/cm3.[0193] When the branched polyolefin wherein the composition of the olefin chain (A) is different from that of the olefinchain (B) is prepared, the terminal modified polyolefin (D) is preferably polypropylene, and in this case, this polypropylenepreferably has a density of usually 0.890 to 0.920 g/cm3, particularly 0.900 to 0.915 g/cm3, and MFR of 0.05 to 1,000g/10 min, particularly 0.1 to 500 g/10 min. When the polypropylene is a copolymer, the content of the copolymerizedcomponent is desired to be usually not more than 10 % by mol, particularly not more than 5 % by mol.

Preparation of branched polyolefin

[0194] The reaction of the functional group-containing polyolefin (C) with the terminal modified polyolefin (D) is carriedout by, for example, contacting the functional group-containing polyolefin (C) with the terminal modified polyolefin (D)under stirring. In this case, it is preferable that the contact is performed in a state where the functional group-containingpolyolefin (C) and the terminal modified polyolefin (D) are molten or in a state where at least a part of the functionalgroup-containing polyolefin (C) and at least a part of the terminal modified polyolefin (D) are dissolved in an organicsolvent, and it is more preferable that the contact is performed in a state where the functional group-containing polyolefin(C) and the terminal modified polyolefin (D) are completely dissolved in an organic solvent.[0195] Examples of the organic solvents employable include aliphatic hydrocarbons, such as hexane, heptane anddecane; aromatic hydrocarbons, such as benzene, toluene and xylene; halogen-containing hydrocarbons, such asmethylene chloride and dichlorobenzene; and hetero atom-containing hydrocarbons, such as dimethyl sulfoxide and

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dimethylformamide.[0196] This reaction is carried out at a temperature of usually 20 to 250°C, preferably 40 to 200°C, for 1 minute to 24hours, preferably 5 minutes to 12 hours.

Thermoplastic resin composition

[0197] The thermoplastic resin composition of the invention comprises the branched polyolefin and a thermoplasticresin other than the branched polyolefin, and contains the branched polyolefin in a content of 0.01 to 50 % by weight,preferably 0.1 to 30 % by weight, more preferably 1 to 25 % by weight.

Thermoplastic resin

[0198] As the thermoplastic resin, at least one thermoplastic resin selected from polyolefin, polyamide, polyester,polyacetal, polystyrene, an acrylonitrile/butadiene/styrene copolymer (ABS), polymethacrylate, polycarbonate, polyphe-nylene oxide, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, an ethylene/(meth)acrylic ester copolymerand a diene rubber is preferably used in the invention.[0199] Examples of the polyolefins include olefin homopolymers other than the branched polyolefin, such as polyeth-ylene, polypropylene, poly-1-butene, polymethylpentene and polymethylbutene; and olefin copolymers, such as anethylene/α-olefin random copolymer, an ethylene/propylene/diene terpolymer, a propylene/ethylene random copolymer,a propylene/α-olefin random copolymer and a propylene/ethylene/α-olefin terpolymer. Of these, polyethylene, polypro-pylene, an ethylene/α-olefin random copolymer, an ethylene/propylene/diene terpolymer, a propylene/ethylene randomcopolymer and a propylene/α-olefin random copolymer are preferable. When the polyolefin is a polyolefin obtained froman olefin of 3 or more carbon atoms, this polyolefin may be an isotactic polymer or may be a syndiotactic polymer.[0200] As the catalyst for the preparation of the polyolefin, any catalyst publicly known, such as a Ziegler-Natta catalystor a metallocene catalyst, may be used.[0201] Examples of the polyamides include aliphatic polyamides, such as nylon-6, nylon-66, nylon-10, nylon-12 andnylon-46, and aromatic polyamides prepared from aromatic dicarboxylic acids and aliphatic diamines. Of these, nylon-6 is preferable.[0202] Examples of the polyesters include aromatic polyesters, such as polyethylene terephthalate, polyethylenenaphthalate and polybutylene terephthalate, polycaprolactone, and polyhydroxy butyrate. Of these, polyethylene tereph-thalate is preferable.[0203] Examples of the polyacetals include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropional-dehyde and polybutylaldehyde. Of these, polyformaldehyde is particularly preferable.[0204] The polystyrene may be a homopolymer of styrene, or may be a bipolymer of styrene and acrylonitrile, methylmethacrylate, α-methylstyrene or the like, such as an acrylonitrile/styrene copolymer.[0205] As the ABS, one containing constituent units derived from acrylonitrile in a content of 20 to 35 % by mol,constituent units derived from butadiene in a content of 20 to 30 % by mol and constituent units derived from styrene ina content of 40 to 60 % by mol is preferably employed.[0206] As the polymethacrylate, polymethyl methacrylate (PMMA) is preferable.[0207] Examples of the polycarbonates include those obtained from bis(4-hydroxypheny)methane,1,1-bis(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxyphenyl)propane and2,2-bis(4-hydroxyphenyl)butane. Of these, polycarbonate obtained from 2,2-bis(4-hydroxyphenyl)propane is preferable.[0208] As the polyphenylene oxide, poly(2,6-dimethyl-1,4-phenylene oxide) is preferable.[0209] The polyvinyl chloride may be a homopolymer of vinyl chloride, or may be a copolymer of vinyl chloride andvinylidene chloride, acrylic ester, acrylonitrile, propylene or the like.[0210] As the polyvinylidene chloride, a copolymer of vinylidene chloride and vinyl chloride, acrylonitrile, (meth)acrylicester, allyl ester, unsaturated ether, styrene or the like, which contains vinylidene chloride units in a content of not lessthan 85 %, is usually employed.[0211] The polyvinyl acetate maybe a homopolymer of vinyl acetate, or may be a copolymer of vinyl acetate andethylene or vinyl chloride. Of these, preferable is an ethylene/vinyl acetate copolymer[0212] As the ethylene/(meth)acrylic ester copolymer, an ethylene/methyl acrylate copolymer, an ethylene/ethyl acr-ylate copolymer, an ethylene/methyl methacrylate copolymer or an ethylene/ethyl methacrylate copolymer is preferable.[0213] Examples of the diene rubbers include conjugated polydienes, such as polybutadiene, polyisoprene and astyrene/butadiene copolymer of elastomer type that is known as SBR (styrene-butadiene rubber). In these diene rubbers,a part of double bonds in the molecules may be hydrogenated.[0214] The thermoplastic resins mentioned above can be used singly or in combination of two or more kinds.[0215] Of the above thermoplastic resins, preferably used is a polyolefin, a polyester, a polyamide or a polystyrene,

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and more preferably used is a polyolefin. Especially when a polyolefin that is a copolymer having different compositionsis used or when two or more kinds of polyolefins are used in combination, the branched polyolefin is most preferablyused as a compatibilizing agent.[0216] The thermoplastic resin composition of the invention is prepared for the main purpose of allowing the compositionto function as an improver of melt properties of the branched polyolefin and/or a compatibilizing agent for a copolymerhaving different compositions or two or more kinds of polyolefins.[0217] More specifically, effects of improvement in melt properties, such as increase of melt tension or swell ratio,and/or effects of compatibilization such that domain size is reduced in the phase structure can be expected.

Additives

[0218] The thermoplastic resin composition of the invention may contain additives, such as inorganic filler, organicfiller, crystal-nucleating agent, hest stabilizer, weathering stabilizer, antistatic agent, colorant, lubricant, flame retardantand anti-blooming agent, within limits not detrimental to the objects of the invention.

Preparation

[0219] The thermoplastic resin composition of the invention can be prepared by blending the branched polyolefin withthe thermoplastic resin by means of, for example, a ribbon blender, a tumbling blender or a Henschel blender.[0220] The thermoplastic resin composition of the invention can be prepared also by melt kneading the branchedpolyolefin with the thermoplastic resin using a kneading machine such as a Ko-kneader, a Banbury mixer, a Brabender,a single-screw extruder or a twin-screw extruder, a horizontal stirring machine such as a twin-screw stirring machinewith surface renewal action or a twin-screw multi-disc agitator, or a vertical stirring machine such as a double-helicalribbon stirring machine.

EXAMPLES

[0221] The present invention is further described with reference to the following examples, but it should be construedthat the invention is in no way limited to those examples.

Example 1

Preparation of solid titanium catalyst component

[0222] 7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 ml of decane and 35.1 ml (225 mmol) of 2-ethylhexylalcohol were reacted with heating at 130°C for 2 hours to give a homogeneous solution. To the solution, 1.67 g (11.3mmol) of phthalic anhydride was added, and the solution was mixed with stirring at 130°C for 1 hour to dissolve thephthalic anhydride in the homogeneous solution. The resulting homogeneous solution was cooled to room temperature,and to 200ml (1.8 mol) of titanium tetrachloride maintained at -20°C, the whole amount of the homogeneous solutionwas dropwise added over a period of 1 hour. After the dropwise addition was completed, the temperature of the mixedsolution was raised to 110°C over a period of 4 hours. When the temperature reached 110°C, 5.03 ml (18.8 mmol) ofdiisobutyl phthalate (referred to as DIBP) was added, followed by stirring at the same temperature for 2 hours. Subse-quently, the resulting solids were collected by hot filtration and resuspended in 275 ml of titanium tetrachloride, and thesuspension was reacted with heating at 110°C for 2 hours. After the reaction was completed, the solids were collectedagain by hot filtration and thoroughly washed with decane at 110°C and hexane at room temperature until no titaniumcompound liberated in the washing liquid was detected.[0223] The solid titanium catalyst component synthesized by the above process was stored as a hexane slurry, anda part of the solid titanium catalyst component was dried to examine the catalyst composition. The composition of theobtained solid titanium catalyst component exhibited Ti of 2.1 % by weight, C1 of 58 % by weight, Mg of 18 % by weightand DIBP of 10.9 % by weight.

Polymerization of propylene

[0224] A 500 ml glass autoclave was purged with nitrogen, and 250 ml of decane was introduced into the autoclave,followed by replacing nitrogen with propylene. Successively, with passing propylene, the autoclave was heated to 100°Cunder stirring, and 5 mmol of triethylaluminum, 0.5 mmol of cyclohexylmethyldimethoxysilane and 0.1 mmol-Ti in termsof titanium atom of the solid titanium catalyst component were added in this order. The polymerization of propylene wasconducted at 100°C for 1 hour to obtain polypropylene, while the feed rate of propylene was controlled so that the

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unreacted gas did not escape through the bubbler tube equipped at the purge line and the pressure in the reactor wasnot reduced. Subsequently, propylene was replaced with nitrogen.

Preparation of terminal modified polypropylene

[0225] The polymerization slurry was maintained at 100°C, and passing air having been dried by passing throughmolecular sieves at a flow rate of 200 l/hr, the reaction was conducted at the same temperature for 5 hours. After thereaction was completed, the slurry was introduced into a mixed liquid of 2 liters of methanol and 2 liters of acetone, andthe mixture was allowed to stand still for one night. The fibrous polymer sticking to the stirring blade was discarded.[0226] A small amount of hydrochloric acid was added to the slurry given after allowing to stand still, and the mixturewas filtered to obtain a white polymer.[0227] The resulting polymer was washed with methanol and then dried under reduced pressure at 80°C for 10 hoursto obtain 2.5 g of terminal modified polypropylene. It was confirmed by 13C-NMR that the terminal modified polypropylenehad hydroxyl groups at positions of 52 % by mol of one-side-ends. The Mw of the terminal modified polypropylene, asmeasured by GPC, was 170,000.

Reaction of functional group-containing polyolefin with terminal modified polyolefin

[0228] In a 500 ml glass reactor, 0.061 g (0.55 Pmol, maleic anhydride group: 3.1 Pmol) of maleic anhydride-modifiedhomopolypropylene (trade name: ADMER, available from Mitsui Chemicals, Inc., Mw: 110,000, modification fraction:0.5 %), 1.0 g (5.9 Pmol, hydroxyl group: 3.1 Pmol) of the terminal modified polypropylene and 250 ml of toluene wereplaced, followed by stirring at 70°C for 30 minutes and then at 80°C for 4.5 hours.[0229] From the resulting slurry, the solvent was removed by an evaporator, and the residual polymer was dried underreduced pressure at 80°C for 10 hours to recover 1.02 g of the polymer.[0230] The resulting polymer was measured by 13C-NMR, and it was found that all the terminal hydroxyl groups ofthe terminal modified polypropylene were converted into ester bonds and 5.6 olefin chains derived from the terminalmodified polypropylene were linked based on one olefin chain derived from the maleic anhydride-modified homopoly-propylene.

Example 2

Reaction of functional group-containing polyolefin with terminal modified polypropylene

[0231] In a 500 ml glass reactor, 0.099 g (0.76 Pmol) of a maleic anhydride-modified ethylene/propylene copolymer(trade name: TAFMER MP-0610, available from Mitsui Chemicals, Inc., obtained by modification of an ethylene/propylenecopolymer having an ethylene content of 80 % by mol with maleic anhydride, melt flow rate: 0.4 g/10 min, Mw: 130,000,modification fraction: 0.5 %), 1.0 g (5.9 Pmol, hydroxyl group: 3.1 Pmol) of the terminal modified polypropylene preparedin Example 1 and 250 ml of toluene were placed, followed by stirring at 70°C for 30 minutes and then at 80°C for 4.5 hours.[0232] From the resulting slurry, the solvent was removed by an evaporator, and the residual polymer was dried underreduced pressure at 80°C for 10 hours to recover 1.02 g of the polymer. The quantity of the 23°C decane-solublecomponent in the recovered polymer was 8.06 % by weight. The decane-insoluble component at 23°C was subjectedto IR measurement, and as a result, a peak of an ethylene chain was detected in the vicinity of 720 cm-1. The decane-insoluble component at 23°C was subjected to 13C-NMR measurement, and as a result, a peak of an ester bond wasdetected.

Measurement of number of side chains

[0233] The quantities of the decane-soluble component at 23°C in the maleic anhydride-modified ethylene/propylenecopolymer and in the terminal modified polypropylene before the reaction were 97.01 % by weight and 6.01 % by weight,respectively.[0234] If the maleic anhydride-modified ethylene/propylene copolymer and the terminal modified polypropylene hadnot reacted at all, the quantity of the decane-soluble component at 23°C should be 14 % by weight by calculation fromthe following formula.

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[0235] As described above, however, the quantity of the decane-soluble component at 23°C in the reaction productof the maleic anhydride-modified ethylene/propylene copolymer with the terminal modified polypropylene was 8.06 %by weight, so that it can be seen from the following formula that 0.065 g (0.50 Pmol) of PO-A was linked to decane-insoluble PO-B at 23°C.

[0236] Consequently, the number of the olefin chains derived from the terminal modified polypropylene based on oneolefin chain derived from the maleic anhydride-modified ethylene/propylene copolymer is calculated to be 5.8 from thefollowing formula.

Example 3

Synthesis of terminal iodinated polyethylene

[0237] In a 500 ml glass container thoroughly purged with nitrogen, 250 ml of dehydrated toluene was placed, andwith stirring, an ethylene gas (100 l/hr) was passed through for 20 minutes. To the container, a toluene solution of 2.5mmol in terms of Al atom of methylaluminoxane (referred to as "MAO" hereinafter), said solution being obtained byvacuum distillation of toluene from a toluene solution of MAO available from Albemarle Corporation at 40°C and thenadding dehydrated toluene again, and 0.01 mmol of bis[7-{N-(2,4,6-trifluorophenyl) iminomethyl}indolinyl]titanium(IV)dichloride ([7-(2,4,6-F-Ph-N=CH)C8H5N]2TiCl2) were successively added and were stirred for 5 minutes with maintainingthe temperature at 25°C to perform living polymerization. The passing gas was changed to a nitrogen gas (100 l/hr),followed by stirring for 10 minutes. To the resulting polymer solution, a toluene solution of iodine (iodine: 2.5 mmol) wasadded, and stirring was further continued at 25°C for 1 hour. The polymer was precipitated in 1.5 liters of methanol,filtered off and dried to obtain 0.80 g of terminal iodinated polyethylene (Mw: 65,000, Mw/Mn: 1.15).

Synthesis of terminal aminated polyethylene

[0238] In 50 ml of dehydrated toluene, 0.5 g of the terminal iodinated polyethylene obtained above was slurried, andto the slurry was added 27 mg (0.15 mmol) of potassium phthal imide. The mixture was stirred with heating at 80°C for12 hours, followed by addition of 10 ml of hydrazine monohydrate was added, and the mixture was heat-refluxed for 2hours. The reaction solution was cooled to room temperature and was added to 1.0 liter of methanol. The precipitatingpolymer was filtered off and dried to obtain terminal aminated polyethylene. It was confirmed by 1H-NMR and IR analysisthat primary amine was present at positions of 60 % by mol of one-side-ends.

Reaction of functional group-containing polyolefin with terminal modified polyolefin

[0239] ADMER available from Mitsui Chemicals, Inc. (homopolypropylene modified with maleic anhydride, Mw:110,000, modification fraction: 0.5 %) was used as a main chain.[0240] In a 500 ml glass reactor, 0.061 g (0.55 Pmol, maleic anhydride group: 3.1 Pmol) of the above main chain,0.34 g (5.2 Pmol, amino group: 3.1 Pmol) of the above side chain and 250 ml of toluene were placed, followed by stirringat 70°C for 30 minutes and then at 80°C for 4.5 hours. From the resulting slurry, the solvent was removed by an evaporator,and the residual polymer was dried under reduced pressure at 80°C for 10 hours to recover 0.36 g of the polymer.[0241] The resulting polymer was subjected to 13C-NMR measurement, and it was found that all the terminal aminogroups of the side chains were converted into amide bonds and 5.6 side chains were linked based on one main chain.

Claims

1. A branched polyolefin comprisingan olefin chain (A) having, as main constituent units, recurring units obtained from at least one olefin selected fromolefins of 2 to 20 carbon atoms and

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olefin chain (s) (B) having, as main constituent units, recurring units obtained from at least one olefin selected fromolefins of 2 to 20 carbon atoms,whereinthe olefin chain (A) is a functional group-containing polyolefin (C) which is a maleic anhydride-modified polyolefinhaving one or more acid anhydride groups at positions other than both ends, which maleic anhydride-modifiedpolyolefin is prepared by graft modifying a part or the whole of an unmodified polyolefin with maleic acid or itsderivatives,the olefin chain (B) is a terminal modified polyolefin (D) which is a polyolefin having an olefin composition which isthe same as or different from that of the functional group-containing polyolefin (C) and containing at least one groupcapable of reacting with an acid anhydride group at only the position of the chain end,at least one olefin chain (B) per one olefin chain (A) is present,the olefin chain (B) is linked to a position other than both ends of the olefin chain (A) through a bond having acarbonyl group, andthe branched polyolefin is obtained by allowing the functional group-containing polyolefin (C) to react with at leastone terminal modified polyolefin (D).

2. The branched polyolefin as claimed in claim 1, wherein the weight-average molecular weight (Mw) of the olefin chain(B) is not less than 5,000.

3. The branched polyolefin as claimed in claim 1, wherein the bond having a carbonyl group is an ester bond and/oran amide bond.

4. The branched polyolefin as claimed in any one of claims 1 to 3, wherein one of the olefin chain (A) and the olefinchain (B) is a crystalline polyolefin and the other is a non-crystalline polyolefin.

5. The branched polyolefin as claimed in any one of claims 1 to 3, wherein both the olefin chain (A) and the olefin chain(B) are polypropylene.

6. The branched polyolefin as claimed in any one of claims 1 to 3, wherein both the olefin chain (A) and the olefin chain(B) have stereoregularity.

7. A process for preparing the branched polyolefin of any one of claims 1 to 6, comprising allowing the functional group-containing polyolefin (C) to react with at least one terminal modified polyolefin (D).

8. The process for preparing a branched polyolefin as claimed in claim 7, wherein the functional group-containingpolyolefin (C) is a maleic anhydride-modified homopolymer or copolymer of ethylene and/or propylene.

9. The process for preparing a branched polyolefin as claimed in claim 7, wherein the terminal modified polyolefin (D)is a one-side-end modified polyolefin having a group capable of reacting with a carboxyl group or an acid anhydridegroup at only one-side-end.

10. The process for preparing a branched polyolefin as claimed in claim 7, wherein the terminal modified polyolefin (D)is a maleic anhydride-modified homopolymer or copolymer of ethylene and/or propylene.

11. A thermoplastic resin composition containing the branched polyolefin of claim 1 in an amount of 0.01 to 50 % by weight.

Patentansprüche

1. Verzweigtes Polyolefin, umfassendeine Olefinkette (A), die als Hauptaufbaueinheiten Wiederholungseinheiten aufweist, die aus zumindest einem Olefinerhalten sind, das aus Olefinen mit 2 bis 20 Kohlenstoffatomen ausgewählt ist, und(eine) Olefinkette(n) (B), die als Hauptaufbaueinheiten Wiederholungseinheiten aufweist/aufweisen, die aus zumin-dest einem Olefin erhalten sind, das aus Olefinen mit 2 bis 20 Kohlenstoffatomen ausgewählt ist,worindie Olefinkette (A) ein (eine) funktionelle Gruppe(n)-enthaltendes Polyolefin (C) ist, welches ein Maleinsäureanhy-drid-modifiziertes Polyolefin ist, das eine oder mehr Säureanhydridgruppe(n) an Positionen außer den beiden Endenaufweist, wobei das Maleinsäureanhydridmodifizierte Polyolefin hergestellt ist durch Pfropf-Modifizieren eines Teils

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oder der Gesamtheit eines unmodifizierten Polyolefins mit Maleinsäure oder seinen Derivaten,die Olefinkette (B) ein endständig modifiziertes Polyolefin (D) ist, welches ein Polyolefin mit einer Olefinzusammen-setzung ist, die die gleiche ist wie die des (eine) funktionelle Gruppe(n)-enthaltenden Polyolefins (C) oder sichhiervon unterscheidet, und welches an nur der Position am Kettenende zumindest eine Gruppe enthält, die mit einerSäureanhydridgruppe reagieren kann,zumindest eine Olefinkette (B) je einer Olefinkette (A) vorliegt,die Olefinkette (B) mit einer Position, außer den beiden Enden, der Olefinkette (A) durch eine Bindung mit einerCarbonylgruppe verknüpft ist unddas verzweigte Polyolefin erhalten wird, indem das (eine) funktionelle Gruppe(n)-enthaltende Polyolefin (C) mitzumindest einem endständig modifizierten Polyolefin (D) umgesetzt wird.

2. Verzweigtes Polyolefin gemäß Anspruch 1, worin das gewichtsgemittelte Molekulargewicht (Mw) der Olefinkette(B) nicht weniger als 5.000 beträgt.

3. Verzweigtes Polyolefin gemäß Anspruch 1, worin die Bindung mit einer Carbonylgruppe eine Esterbindung und/oder eine Amidbindung ist.

4. Verzweigtes Polyolefin gemäß irgendeinem der Ansprüche 1 bis 3, worin eine von der Olefinkette (A) und derOlefinkette (B) ein kristallines Polyolefin ist und das andere ein nicht-kristallines Polyolefin ist.

5. Verzweigtes Polyolefin gemäß irgendeinem der Ansprüche 1 bis 3, worin sowohl die Olefinkette (A) als auch dieOlefinkette (B) Polypropylen sind.

6. Verzweigtes Polyolefin gemäß irgendeinem der Ansprüche 1 bis 3, worin sowohl die Olefinkette (A) als auch dieOlefinkette (B) Stereoregularität aufweisen.

7. Verfahren zur Herstellung des verzweigten Polyolefins gemäß irgendeinem der Ansprüche 1 bis 6, umfassend eineUmsetzung des (eine) funktionelle Gruppe(n)-enthaltenden Polyolefins (C) mit zumindest einem endständig modi-fizierten Polyolefin (D).

8. Verfahren zur Herstellung eines verzweigten Polyolefins gemäß Anspruch 7, worin das (eine) funktionelle Gruppe(n)-enthaltende Polyolefin (C) ein Maleinsäureanhydrid-modifiziertes Homopolymer oder Copolymer von Ethylenund/oder Propylen ist.

9. Verfahren zur Herstellung eines verzweigten Polyolefins gemäß Anspruch 7, worin das endständig modifiziertePolyolefin (D) ein einseitig endständig modifiziertes Polyolefin ist, das nur an einer Seite eine Gruppe aufweist, diemit einer Carboxylgruppe oder einer Säureanhydridgruppe reagieren kann.

10. Verfahren zur Herstellung eines verzweigten Polyolefins gemäß Anspruch 7, worin das endständig modifiziertePolyolefin (D) ein Maleinsäureanhydrid-modifiziertes Homopolymer oder Copolymer von Ethylen und/oder Propylenist.

11. Thermoplastische Harzzusammensetzung, enthaltend das verzweigte Polyolefin gemäß Anspruch 1 in einer Mengevon 0,01 bis 50 Gew.-%.

Revendications

1. Polyoléfine ramifiée comprenantune chaîne oléfinique (A) ayant, comme unités constitutives principales, des unités récurrentes obtenues à partird’au moins une oléfine choisie parmi des oléfines de 2 à 20 atomes de carbone etune (des) chaîne(s) oléfinique(s) (B) ayant, comme unités constitutives principales, des unités récurrentes obtenuesà partir d’au moins une oléfine choisie parmi des oléfines de 2 à 20 atomes de carbone,dans laquellela chaîne oléfinique (A) est une polyoléfine contenant un groupe fonctionnel (C) qui est une polyoléfine modifiéeavec un anhydride maléique ayant un ou plusieurs groupes anhydride acide à des positions autres que les deuxextrémités, laquelle polyoléfine modifiée avec un anhydride maléique est préparée en modifiant par greffage unepartie ou la totalité d’une polyoléfine non modifiée avec de l’acide maléique ou ses dérivés,

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la chaîne oléfinique (B) est une polyoléfine modifiée à sa terminaison (D) qui est une polyoléfine ayant une compo-sition oléfinique qui est identique à ou différente de celle de la polyoléfine contenant un groupe fonctionnel (C) etcontenant au moins un groupe apte à réagir avec un groupe anhydride acide à uniquement la position de l’extrémitéde la chaîne,au moins une chaîne oléfinique (B) pour une chaîne oléfinique (A) est présente,la chaîne oléfinique (B) est liée à une position autre que les deux extrémités de la chaîne oléfinique (A) par l’inter-médiaire d’une liaison ayant un groupe carbonyle, etla polyoléfine ramifiée est obtenue en laissant la polyoléfine contenant un groupe fonctionnel (C) réagir avec aumoins une polyoléfine modifiée à sa terminaison (D).

2. Polyoléfine ramifiée selon la revendication 1, dans laquelle le poids moléculaire moyen en poids (Mw) de la chaîneoléfinique (B) n’est pas moins de 5 000.

3. Polyoléfine ramifiée selon la revendication 1, dans laquelle la liaison ayant un groupe carbonyle est une liaisonester et/ou une liaison amide.

4. Polyoléfine ramifiée selon l’une quelconque des revendications 1 à 3, dans laquelle l’une de la chaîne oléfinique(A) et de la chaîne oléfinique (B) est une polyoléfine cristalline et l’autre est une polyoléfine non cristalline.

5. Polyoléfine ramifiée selon l’une quelconque des revendications 1 à 3, dans laquelle la chaîne oléfinique (A) et lachaîne oléfinique (B) sont toutes les deux un polypropylène.

6. Polyoléfine ramifiée selon l’une quelconque des revendications 1 à 3, dans laquelle la chaîne oléfinique (A) et lachaîne oléfinique (B) ont toutes les deux une stéréorégularité.

7. Procédé pour préparer la polyoléfine ramifiée selon l’une quelconque des revendications 1 à 6, comprenant delaisser la polyoléfine contenant un groupe fonctionnel (C) réagir avec au moins une polyoléfine modifiée à saterminaison (D).

8. Procédé pour préparer une polyoléfine ramifiée selon la revendication 7, dans lequel la polyoléfine contenant ungroupe fonctionnel (C) est un homopolymère ou un copolymère modifié avec un anhydride maléique d’éthylèneet/ou de propylène.

9. Procédé pour préparer une polyoléfine ramifiée selon la revendication 7, dans lequel la polyoléfine modifiée à saterminaison (D) est une polyoléfine modifiée à une seule extrémité ayant un groupe apte à réagir avec un groupecarboxyle ou un groupe anhydride acide à une seule extrémité.

10. Procédé pour préparer une polyoléfine ramifiée selon la revendication 7, dans lequel la polyoléfine modifiée à saterminaison (D) est un homopolymère ou un copolymère modifié avec un anhydride maléique d’éthylène et/ou depropylène.

11. Composition de résine thermoplastique contenant la polyoléfine ramifiée selon la revendication 1 dans une quantitéde 0,01 à 50% en poids.

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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the Europeanpatent document. Even though great care has been taken in compiling the references, errors or omissions cannot beexcluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• EP 0366412 A [0006]• EP 0856541 A [0007]

• JP 2276807 A [0126]